Biarylhydroxythiophene Group IV transition metal polymerization catalyst with chain transfer ability

Abstract

A catalyst system comprising a chain transfer agent and a metal-ligand complex according to formula (I).

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 62 / 782,856, filed on December 20, 2018, the entire disclosure of which is hereby incorporated by reference. Technical Field

[0003]

[0014] Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more particularly to olefin polymerization processes incorporating catalyst systems comprising chain shuttling agents. Background Art

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

[0005] Ethylene-based polymers and propylene-based polymers are manufactured for various products. Polyethylene and polypropylene polymerization processes may differ in many aspects to produce a variety of resulting polyethylene resins with different physical properties that make the various resins suitable for different applications. Ethylene monomer and optionally one or more comonomers are present in a liquid diluent (such as a solvent), such as an alkane or isoalkane, for example, isobutane. Hydrogen can also be added to the reactor. The catalyst system for producing ethylene-based polymers can generally include a chromium-based catalyst system, a Ziegler-Natta catalyst system and / or a molecular (metallocene or non-metallocene (molecular)) catalyst system. The reactants in the diluent and catalyst system circulate around the reactor at an elevated polymerization temperature, thereby producing ethylene-based homopolymers or copolymers. Periodically or continuously, a portion of the reaction mixture comprising the polyethylene product dissolved in the diluent and unreacted ethylene and one or more optional comonomers are removed from the reactor. The reaction mixture can be processed to remove the polyethylene product from the diluent and unreacted reactants when removed from the reactor, wherein the diluent and unreacted reactants are typically recycled back into the reactor. Alternatively, the reaction mixture can be sent to a second reactor connected in series to the first reactor, in which second reactor a second polyethylene fraction can be produced.Despite research into developing catalyst systems suitable for olefin polymerization, such as polyethylene or polypropylene polymerization, there remains a need to improve the efficiency of catalyst systems capable of producing polymers having high molecular weight and narrow molecular weight distribution. Summary of the Invention

[0006] Despite the availability of currently available olefin polymerization catalyst systems, there remains a need for high temperature (approximately 120°C-150°C) polymerization catalysts having improved molecular properties that promote the production of high molecular weight (Mw) polymers with narrow polydispersity (PDI), high comonomer incorporation (i.e., greater than 20%), and the ability to participate in chain transfer with diethylzinc (DEZ) to produce olefin block copolymers with high chain transfer rates (i.e., Ca ≥ 1.0). Olefin block copolymers (OBCs) exhibit excellent property differentiation that cannot be achieved through polymer blending.

[0007] There is a need to improve the ability of olefin polymerization catalysts to chain transfer or shuttling with chain transfer agents (also known as transfer agents) and hard segment catalysts.

[0008] Embodiments of the present disclosure include a catalyst system comprising a metal-ligand complex according to formula (I) and a chain transfer agent. Metal-ligand complex according to formula (I):

[0009]

[0010] In formula (I), M is a metal selected from titanium, zirconium or hafnium, the metal having a formal oxidation state of +2, +3 or +4. Each X is a monodentate or bidentate ligand independently selected from the following: unsaturated (C2-C 20 ) hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) alkyl, (C6-C 50 )aryl, (C6-C 50 ) heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 )Diene, halogen, -OR C 、-N(R N )2 and -NCOR C ; and subscript n is 1 or 2. Each Y is oxygen, sulfur or NR N .

[0011] In formula (I), each R 1 Selected from (C1-C 50 )alkyl, (C1-C 50 ) heteroalkyl, (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、RC 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. Each R N 、R C and R P Independently selected from (C1-C 20 )alkyl, (C1-C 20 ) heteroalkyl and -H. Q is (C1-C 12 )alkylene, (C1-C 12 )heteroalkylene, (-CH2Si(R Q )2CH2-)、(-CH2CH2Si(R Q )2CH2CH2-)、(-CH2Ge(R Q )2CH2-) or (-CH2CH2Ge(R Q )2CH2CH2-), where R Q is (C1-C 20 )alkyl.

[0012] In formula (I), for each individual ring containing groups z1 and z2, each of z1 and z2 is independently selected from sulfur, oxygen, -N(R C )- and -C(R C )-, provided that at least one of z1 and z2 is sulfur. Each R 4a 、R 5a 、R 6a and R 7a Independently selected from (C1-C 50 )alkyl, (C1-C 50 ) heteroalkyl, (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)-, halogen and -H, wherein optionally R 4a and R 5a or R 5a and R 6a or R 6a and R 7a They may be covalently linked to form an aromatic ring or a non-aromatic ring. C 、R N and R P Independently selected from (C1-C 20 )alkyl, (C1-C 20 ) a group consisting of a heteroalkyl group and -H. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 A four-step synthetic scheme for the synthesis of ligand 1 (L-1) is depicted.

[0014] Figure 2 A two-step synthetic scheme for the synthesis of ligands 2-3 (L-2 to L-3) is depicted, where the reagents in the first step vary depending on the ligand.

[0015] Figure 3 A three-step synthetic scheme for the synthesis of ligand 5 (L-5) is depicted.

[0016] Figure 4 is a graph showing the change in polymer molecular weight as a function of the amount of chain shuttling agent in Procatalyst 1.

[0017] Figure 5 is a graph showing the change in polymer molecular weight as a function of the amount of chain shuttling agent in the primary catalyst 2.

[0018] Figure 6 This is a graph showing the change in polymer molecular weight as a function of the amount of chain shuttling agent in the primary catalyst 4.

[0019] Figure 7 This is a graph showing the change in polymer molecular weight as a function of the amount of chain shuttling agent in the primary catalyst 5.

[0020] Figure 8 This is a graph showing the change in polymer molecular weight as a function of the amount of chain shuttling agent in the primary catalyst 6.

[0021] Figure 9 is a graph showing the change in polymer molecular weight as a function of the amount of chain shuttling agent in the primary catalyst 12. DETAILED DESCRIPTION

[0022] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure can be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure.

[0023] Common abbreviations are listed below:

[0024] R, Z, M, X and n: as defined above; Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; i-Pr: isopropyl; t-Bu: tert-butyl; t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl); Tf: trifluoromethanesulfonate; CV: column volume (for column chromatography); EtOAc: ethyl acetate; Pd(dppf)Cl2: [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride; PhMe: toluene; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; GC: gas chromatography; LC: liquid chromatography; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimole; mL: milliliter; M: mole; min or mins: minutes; h or hrs: hours; d: day; TLC: thin layer chromatography; rpm: revolutions per minute.

[0025] The term "independently selected from" is used herein to indicate that, for example, R 1 、R 2 、R 3 、R 4 and R 5 The R groups may be the same or different (e.g., R 1 、R 2 、R 3 、R 4 and R 5 can be substituted alkyl, or R 1 and R 2 may be a substituted alkyl group, and R 3 The chemical names associated with R groups are intended to convey chemical structures that are generally recognized in the art as corresponding to the chemical structure of the chemical name. Thus, the chemical names are intended to supplement and illustrate, rather than exclude, structural definitions known to those skilled in the art.

[0026] The term "procatalyst" 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 procatalyst in a manner that converts the procatalyst into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms.

[0027] When used to describe certain chemical groups containing carbon atoms, the form "(C x -C y)" means that the unsubstituted form of the chemical group has x to y carbon atoms, inclusive. For example, (C1-C 50 ) alkyl is an alkyl group having 1 to 50 carbon atoms in an unsubstituted form. In some embodiments and general structures, certain chemical groups may be replaced by one or more substituents (such as R S ) is replaced by the parenthetical phrase “(C x -C y )” defined by R S The substituted chemical group may contain more than y carbon atoms, depending on the number of any group R S For example, “using only one R S Group-substituted (C1-C 50 )alkyl, wherein R S is a phenyl group (-C6H5)" can contain from 7 to 56 carbon atoms. Therefore, in general, when the parenthetical phrase "(C x -C y )" is replaced by one or more carbon-containing substituents R S When substituted, both x and y are added to the substituent R from all carbon atoms S The combined sum of the number of carbon atoms is used to determine the minimum and maximum total number of carbon atoms in a chemical group.

[0028] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom in the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S The term "persubstituted" means that each hydrogen atom (H) bonded to a carbon atom or heteroatom in the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S ) is replaced by a substituted alkyl group. The term "polysubstituted" means that at least two but fewer than all hydrogen atoms bonded to carbon atoms or heteroatoms in the corresponding unsubstituted compound or functional group are replaced by substituents. The term "-H" means a hydrogen or hydrogen group covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless expressly specified otherwise.

[0029] The term "(C1-C 50 )hydrocarbyl" means a hydrocarbon group having 1 to 50 carbon atoms, and the term "(C1-C 50 ) alkylene group" means a hydrocarbon diradical having 1 to 50 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (having three carbon atoms or more and including monocyclic and polycyclic, fused and non-fused polycyclic and bicyclic) or acyclic, and is supported by one or more R S Replaced or not replaced.

[0030] In the present disclosure, (C1-C 50 ) The hydrocarbon group may be unsubstituted or substituted (C1-C 50 )alkyl, (C3-C 50 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 )alkylene, (C6-C 40 )aryl or (C6-C 20 )aryl-(C1-C 20 )alkylene (such as phenyl (-CH2-C6H5)).

[0031] The term "(C1-C 50 )alkyl" and "(C1-C 18 )alkyl" refers to a group which is unsubstituted or substituted with one or more R S Substituted saturated straight chain or branched hydrocarbon groups having 1 to 50 carbon atoms and saturated straight chain or branched hydrocarbon groups having 1 to 18 carbon atoms. 50 Examples of alkyl groups are unsubstituted (C1-C 20 ) alkyl; unsubstituted (C1-C 10 )alkyl; unsubstituted (C1-C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Substituted (C1-C 40 Examples of alkyl groups are substituted (C1-C 20 )alkyl, substituted (C1-C 10 )alkyl, trifluoromethyl and [C 45 ] alkyl. The term "[C 45 ] alkyl" means that there are up to 45 carbon atoms in the group (including substituents) and are, for example, each of which is supported by one R S Substituted (C 27 -C 40 ) alkyl, said one R S is a (C1-C5)alkyl group. Each (C1-C5)alkyl group may be a methyl group, a trifluoromethyl group, an ethyl group, a 1-propyl group, a 1-methylethyl group or a 1,1-dimethylethyl group. 10 Examples of alkyl groups include all butyl, pentyl, hexyl, heptyl, nonyl, and decyl isomers.

[0032] The term "(C6-C 50 ) aryl" means an unsubstituted or substituted (one or more R S) substituted monocyclic, bicyclic or tricyclic aromatic hydrocarbon groups, wherein at least 6 to 24 carbon atoms are aromatic ring carbon atoms. Monocyclic aromatic hydrocarbon groups contain one aromatic ring; bicyclic aromatic hydrocarbon groups have two rings; and tricyclic aromatic hydrocarbon groups have three rings. When bicyclic or tricyclic aromatic hydrocarbon groups are present, at least one of the rings of the group is aromatic. The other one or more rings of the aromatic group may independently be fused or non-fused and be aromatic or non-aromatic. Unsubstituted (C6-C 50 Examples of aryl groups include: unsubstituted (C6-C 20 ) aryl, unsubstituted (C6-C 18 )aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C6-C 40 Examples of aryl groups include: substituted (C1-C 20 ) aryl; substituted (C6-C 18 )aryl; 2,4-bis([C 20 ] alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-on-1-yl.

[0033] The term "(C3-C 50 ) cycloalkyl" means a cycloalkyl having 3 to 50 carbon atoms which is unsubstituted or substituted with one or more R S Substituted saturated cyclic hydrocarbon groups. Other cycloalkyl groups (for example, (C x -C y )cycloalkyl) is similarly defined as having x to y carbon atoms and being unsubstituted or substituted with one or more R S Substituted. Unsubstituted (C3-C 40 Examples of cycloalkyl groups are unsubstituted (C3-C 20 )cycloalkyl, unsubstituted (C3-C 10 )cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. Substituted (C3-C 40 Examples of cycloalkyl groups are substituted (C3-C 20 )cycloalkyl, substituted (C3-C 10 )cycloalkyl, cyclopentanone-2-yl and 1-fluorocyclohexyl.

[0034] (C1-C 50 Examples of alkylene groups include unsubstituted or substituted (C6-C 50 )arylene, (C3-C 50 )cycloalkylene and (C1-C 50)alkylene (e.g., (C1-C 20 ) alkylene). The diradicals can be on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or more than two intermediate carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-diradicals, 1,3-diradicals, 1,4-diradicals, or α,ω-diradicals and other 1,2-diradicals. α,ω-diradicals are diradicals with the largest carbon backbone spacing between the radical carbons. (C2-C 20 Some examples of alkylene α,ω-diyl groups include ethane-1,2-diyl (ie, -CH2CH2-), propane-1,3-diyl (ie, -CH2CH2CH2-), 2-methylpropane-1,3-diyl (ie, -CH2CH(CH3)CH2-). (C6-C 50 Some examples of )arylene α,ω-diyl include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0035] The term "(C1-C 50 ) alkylene means an unsubstituted or substituted group having 1 to 50 carbon atoms. S Substituted saturated straight or branched chain diradicals (ie, the groups are not on ring atoms). Unsubstituted (C1-C 50 Examples of alkylene groups are unsubstituted (C1-C 20 )alkylene, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3 and -(CH2)4C*(H)(CH3), wherein "C * " represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl group. Substituted (C1-C 50 Examples of alkylene groups are substituted (C1-C 20 )alkylene, -CF2-, -C(O)- and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted n-1,20-eicosene). Since the two R S Can be put together to form (C1-C 18 ) alkylene, thus substituted (C1-C 50 Examples of the alkylene group also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0036] The term "(C3-C 50 ) cycloalkylene means a cycloalkylene group having 3 to 50 carbon atoms which is unsubstituted or substituted with one or more R S Substituted cyclic diradicals (ie, the groups are on ring atoms).

[0037] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), S(O)2, Si(R C )2、P(R P )、N(R N ),-N=C(R C )2、-Ge(R C )2- or -Si(R C )-, where each R C and R P is unsubstituted (C1-C 18 )alkyl or -H, and wherein each R N is unsubstituted (C1-C 18 )hydrocarbon group. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by a heteroatom. 50 )heteroalkyl" means a heteroalkyl group having 1 to 50 carbon atoms, and the term "(C1-C 50 ) heteroalkylene" means a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1-C 50 ) heteroalkyl or (C1-C 50 The heteroalkylene group has one or more heteroatoms. The radicals of the heteroalkylene group may be on carbon atoms or heteroatoms. The two radicals of the heteroalkylene group may be on a single carbon atom or on a single heteroatom. In addition, one of the two radicals of the diradical may be on a carbon atom and the other may be on a different carbon atom; one of the two radicals may be on a carbon atom and the other on a heteroatom; or one of the two radicals may be on a heteroatom and the other on a different heteroatom. Each (C1-C 50 ) heteroalkyl and (C1-C 50 ) heteroalkylene groups may be unsubstituted or substituted with (one or more R S ) substituted, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0038] (C1-C 50 )Heteroalkyl may be unsubstituted or substituted. (C1-C 50 Non-limiting examples of heteroalkyl groups include (C1-C 50 ) heteroalkyl, (C1-C50 )alkyl-O-, (C1-C 50 )alkyl-S-, (C1-C 50 )alkyl-S(O)-, (C1-C 50 )alkyl-S(O)2-, (C1-C 50 )alkyl-Si(R C )2-、(C1-C 50 )alkyl-N(R N )-、(C1-C 50 )alkyl-P(R P )-、(C2-C 50 )heterocycloalkyl, (C2-C 19 )heterocycloalkyl-(C1-C 20 )alkylene, (C3-C 20 )cycloalkyl-(C1-C 19 )heteroalkylene, (C2-C 19 )heterocycloalkyl-(C1-C 20 )heteroalkylene, (C1-C 50 )heteroaryl, (C1-C 19 )heteroaryl-(C1-C 20 )alkylene, (C6-C 20 )aryl-(C1-C 19 )heteroalkylene or (C1-C 19 )heteroaryl-(C1-C 20 ) heteroalkylene.

[0039] The term "(C4-C 50 ) heteroaryl" means an unsubstituted or substituted (one or more R S ) substituted monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon groups. Monocyclic heteroaromatic hydrocarbon groups contain one heteroaromatic ring; bicyclic heteroaromatic hydrocarbon groups have two rings; and tricyclic heteroaromatic hydrocarbon groups have three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon group is present, at least one of the rings in the group is heteroaromatic. The other one or more rings of the heteroaromatic group can independently be fused or non-fused and be aromatic or non-aromatic. Other heteroaryl groups (e.g., typically (C x -C y ) heteroaryl, such as (C4-C 12 ) heteroaryl) is similarly defined as having x to y carbon atoms (e.g., 4 to 12 carbon atoms) and being unsubstituted or substituted with one or more than one R SSubstitution. The monocyclic heteroaromatic hydrocarbon group is a 5-membered ring or a 6-membered ring. The 5-membered ring monocyclic heteroaromatic hydrocarbon group has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3; and each heteroatom can be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon groups include: pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thien-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. A 6-membered monocyclic heteroaromatic hydrocarbon group has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatoms can be N or P. Examples of 6-membered heteroaromatic hydrocarbon groups include: pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. A bicyclic heteroaromatic hydrocarbon group can be a fused 5,6-ring system or a 6,6-ring system. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon groups are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon groups are quinolin-2-yl; and isoquinolin-1-yl. A tricyclic heteroaromatic hydrocarbon group can be a fused 5,6,5-ring system; a 5,6,6-ring system; a 6,5,6-ring system; or a 6,6,6-ring system. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridin-9-yl.

[0040] The term "(C1-C 50 ) heteroalkyl" means a saturated straight or branched chain group containing from one to fifty carbon atoms and one or more heteroatoms. The term "(C1-C 50 ) heteroalkylene" means a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of the heteroalkyl or heteroalkylene group may include Si(R C )3、Ge(R C )3、Si(R C )2、Ge(R C )2、P(R P )2、P(R P )、N(R N )2、N(R N ), N, O, OR C , S, SR C, S(O) and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is unsubstituted or replaced by one or more R S replace.

[0041] Unsubstituted (C2-C 40 Examples of the heterocycloalkyl group include unsubstituted (C2-C 20 ) heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridine-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxane-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thioxo-cyclononyl and 2-aza-cyclodecyl.

[0042] The term "halogen atom" or "halogen" refers to a group of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom: a fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ) or iodide ion (I - ).

[0043] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in groups containing heteroatoms) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. S In the case of substitution, one or more double and / or triple bonds may optionally be present in the substituent R S The term "unsaturated" means containing one or more carbon-carbon double bonds or carbon-carbon triple bonds or (in groups containing heteroatoms) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds or carbon-silicon double bonds, excluding those that may be present in substituents R S (if any) or double bonds (if any) in an aromatic ring or a heteroaromatic ring.

[0044] Embodiments of the present disclosure include catalyst systems comprising a metal-ligand complex according to formula (I) and a chain shuttling (chain transfer) agent. Metal-ligand complex according to formula (I):

[0045]

[0046] In formula (I), M is a metal selected from titanium, zirconium or hafnium, the metal having a formal oxidation state of +2, +3 or +4. Each X is a monodentate or bidentate ligand independently selected from the following: unsaturated (C2-C 20 ) hydrocarbons, unsaturated (C2-C 50) heterohydrocarbons, (C1-C 50 ) alkyl, (C6-C 50 )aryl, (C6-C 50 ) heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 )Diene, halogen, -OR C 、-N(R N )2 and -NCOR C ; and subscript n is 1 or 2. Each Y is oxygen, sulfur or NR N .

[0047] In formula (I), each R 1 Selected from (C1-C 50 )alkyl, (C1-C 50 ) heteroalkyl, (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)-, halogen and -H. Each R N 、R C and R P Independently selected from (C1-C 20 )alkyl, (C1-C 20 ) a group consisting of a heteroalkyl group and -H.

[0048] In some embodiments of Formula (I), Q is (C1-C 12 )alkylene, (C1-C 12 )heteroalkylene, (-CH2Si(R Q )2CH2-)、(-CH2CH2Si(R Q )2CH2CH2-)、(-CH2Ge(R Q )2CH2-) or (-CH2CH2Ge(R Q )2CH2CH2-), where R Qis (C1-C 20 ) alkyl. In one or more embodiments, each R Q Selected from branched, straight or cyclic (C1-C 20 ) alkyl. In various embodiments, each R Q is selected from methyl, ethyl, 2-propyl (also known as isopropyl), tert-butyl, 1-butyl, 2-butyl, 2-methylpropyl (also known as isobutyl), pentyl, hexyl, cyclohexyl, heptyl, octyl, n-octyl, tert-octyl or nonyl.

[0049] In formula (I), for each individual ring containing groups z1 and z2, each of z1 and z2 is independently selected from sulfur, oxygen, -N(R C )- and -C(R C )-, provided that at least one of z1 and z2 is sulfur. Each R 4a 、R 5a 、R 6a and R 7a Independently selected from (C1-C 50 )alkyl, (C1-C 50 ) heteroalkyl, (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)-, halogen and -H, wherein optionally R 4a and R 5a or R 5a and R 6a or R 6a and R 7a They may be covalently linked to form an aromatic ring or a non-aromatic ring. C 、R N and R P Independently selected from (C1-C 20 )alkyl, (C1-C 20) heteroalkyl and -H. Each Y is oxygen, sulfur or NR N .

[0050] In some embodiments of the polymerization method of the present disclosure, a second catalyst may be included. The second catalyst may have a structure according to formula (I).

[0051] In some embodiments, each R 1 Can be selected from carbazole, S or more than one R S Substituted carbazol-9-yl; phenyl, replaced by R S or more than one R S substituted phenyl; anthracenyl, or R S or more than one R S Substituted anthracen-9-yl, wherein R S It can be (C1-C 30 ) alkyl. In other embodiments, each R 1 It can be selected from carbazol-9-yl; 3,6-di-tert-butylcarbazol-9-yl; 2,7-di-tert-butylcarbazol-9-yl; 3,6-bis-(2,4,6-trimethylphenyl)carbazol-9-yl; 3,6-bis-(2,4,6-triisopropylphenyl)carbazol-9-yl; 3,6-bis-(3,5-di-tert-butylphenyl)carbazol-9-yl; anthracene-9-yl; 3,5-di-tert-butylphenyl; 1,1':3',1"-terphenyl-5'-yl; 3,3",5,5"-tetra-tert-butyl-1,1':3',1"-terphenyl-5'-yl; 3,5-diphenylphenyl; 2,4,6-trimethylphenyl; 2,4,6-tri(isopropyl)phenyl; or 3,5-di-tert-butylphenyl. In some embodiments, each R S Independently selected from methyl, ethyl, propyl, 2-propyl, n-butyl, tert-butyl, n-octyl or tert-octyl.

[0052] In one or more embodiments of the catalyst system of the metal-ligand complex according to formula (I), R 1 may be selected from a group having formula (II), a group having formula (III) or a group having formula (IV):

[0053]

[0054] When present in the metal-ligand complex of formula (I) as part of a group having formula (II), formula (III) or formula (IV), the group R of the metal-ligand complex of formula (I) 31-35 、R 41-48 and R 51-59 Each independently selected from (C1-C 40 )alkyl, (C1-C 40) heteroalkyl, Si(R C )3、P(R P )2、N(R N )2、OR C SR C 、NO2、CN、CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R N )2NC(O)-, halogen, hydrogen (-H) or a combination thereof. Each R C 、R P and R N are independently unsubstituted (C1-C 18 )alkyl, (C1-C 30 ) heteroalkyl or -H.

[0055] When present in the metal-ligand complex of formula (I) as part of a group having formula (II), formula (III) or formula (IV), the group R of the metal-ligand complex of formula (I) 31-35 、R 41-48 and R 51-59 Each is independently selected from methyl, ethyl, propyl, 2-propyl (also known as isopropyl), tert-butyl, tert-octyl, n-octyl, phenyl, 3,5-di-tert-butyl-phenyl, 2,4,6-tri-tert-butyl-phenyl.

[0056] In some embodiments, the chemical groups (e.g., X, R 1 、R 31-59 In other embodiments, any or all of the chemical groups X, R, A, and Y) of the metal-ligand complex of formula (I) may be unsubstituted. 1 、R 31-59 None, any or all of z, A and Y may be replaced by one or more than one R S Replace. When two or more R S When combined with the same chemical group of the metal-ligand complex of formula (I), the individual R S can be bound to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. 1 、R 31-59 None, any, or all of Z can be S Complete replacement. SIn fully substituted chemical groups, individual R S They may all be the same or may be independently selected.

[0057] Each R in the metal-ligand complex of formula (I) 1 are selected independently of each other. For example, a group R 1 can be selected from groups having formula (II), (III) or (IV), and another group R 1 It can be (C1-C 40 ) a hydrocarbon group; or a group R 1 can be selected from groups having formula (II), (III) or (IV), and another group R 1 Can be selected from R 1 The two groups R are the same or different groups having formula (II), (III) or (IV). 1 It may be a group of formula (II) wherein the group R 31 -35 In each R 1 In other examples, the two groups R 1 It may be a group of formula (III) wherein the group R 41 -48 In each R 1 the same or different; or two groups R 1 can be a group of formula (IV) wherein the group R 51-59 In each R 1 Same or different.

[0058] In some embodiments of Formula (I), each R 1 Can be selected from carbazole, S or more than one R S Substituted carbazol-9-yl, phenyl, R S or more than one R S Substituted phenyl, anthracenyl, R S or more than one R S substituted anthracene-9-yl, naphthyl or R S or more than one R S Substituted naphthyl, wherein R S It can be (C1-C 30 ) alkyl, wherein R S Can be selected from (C1-C 12 )alkyl, (C6-C 15 )aryl or (C3-C 12 )cycloalkyl.

[0059] In some embodiments of Formula (I), each R 1is a group having formula (II), and R 41–48 At least one of (C1-C 40 )alkyl, (C1-C 40 ) heteroalkyl, -Si(R C )3. -OR C 、-SR C , -NO2, -CN, -CF3 or halogen substituted.

[0060] In one or more embodiments of formula (I), each R 1 is a group having formula (II); and (1) R 42 and R 47 (C1-C 20 )alkyl, -Si(R C )3, -CF3 or halogen substituted, and R 43 and R 46 is -H; or (2) R 43 and R 46 (C1-C 20 )alkyl, -Si(R C )3, -CF3 or halogen substituted, and R 42 and R 47 Yes -H.

[0061] In various embodiments of Formula (I), each R 1 is a group having formula (III); and R 51–59 is -H. In other embodiments of (I), each R 1 is a group having formula (III); and R 51–59 At least one of (C1-C 40 )alkyl, (C1-C 40 ) heteroalkyl, -Si(R C )3. -OR C 、-SR C , -NO2, -CN, -CF3 or halogen substituted.

[0062] In some embodiments of the metal-ligand catalyst according to formula (I), R 1Selected from 3,5-di-tert-butylphenyl; 2,4,6-trimethylphenyl; 2,4,6-triisopropylphenyl; 3,5-diisopropylphenyl; carbazolyl; carbazol-9-yl, 1,2,3,4-tetrahydrocarbazolyl; 1,2,3,4,5,6,7,8-octahydrocarbazolyl; 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-octahydrophenanthryl; 1,2,3,4-tetrahydronaphthyl; 2,6-dimethylphenyl; 2,6-diisopropylphenyl; 3,5-diphenylphenyl; 1-naphthyl; 2-methyl-1-naphthyl; 2-naphthyl; 1,2,3,4-tetrahydronaphth-5-yl; 1,2,3,4-tetrahydronaphth-6-yl; anthracen-9-yl; 1,2,3,4-tetrahydroanthracen-9-yl; 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl; 1,2,3,4,5,6,7,8-octahydrophenanthrene-9-yl; indolyl; dihydroindolinyl; quinolyl; 1,2,3,4-tetrahydroquinolyl; isoquinolyl; 1,2,3,4-tetrahydroisoquinolyl.

[0063] In various embodiments of Formula (I), Z1 is sulfur. In other embodiments of Formula (I), Z2 is sulfur. In some embodiments, Y is oxygen. In one or more embodiments, Y is oxygen and Z1 is sulfur.

[0064] In some embodiments of Formula (I), each R 4a 、R 5a 、R 6a and R 7a are independently (C1-C 20 )alkyl, (C1-C 10 )alkyl, (C6-C 20 ) aryl, or (C6-C 20 ) aryl. In one or more embodiments, each R 4a 、R 5a 、R 6a and R 7a is selected from methyl, ethyl, propyl, 2-propyl, 2-methylpropyl, n-butyl, tert-butyl (also known as 1,1-dimethylethyl), pentyl, hexyl, 1-cyclohexyl, heptyl, tert-octyl (also known as 1,1,3,3-tetramethylbutyl), n-octyl, nonyl, chloro, fluoro, methoxy or -H.

[0065] In some embodiments of formula (I), the catalyst system may comprise a metal-ligand complex according to formula (I), wherein 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 R )-or-C(R R )-, and at least one of z1 or z2 is -C(R R )-. Any two R bonded to adjacent atoms R The groups are optionally linked. In some embodiments, for each individual ring containing groups z1 and z2, one of z1 and z2 is a sulfur atom and the other of z1 and z2 is -C(H)-.

[0066] M in the metal-ligand complex of formula (I) may be a transition metal such as titanium (Ti), zirconium (Zr) or hafnium (Hf), and the formal oxidation state of the transition metal may be +2, +3 or +4. (X) refers to the number of ligands X bound or associated with the metal M. n The subscript n is an integer of 1, 2 or 3.

[0067] The M in the metal-ligand complex of formula (I) can be derived from a metal precursor that is subsequently subjected to a single-step or multi-step synthesis for the preparation of the metal-ligand complex. Suitable metal precursors can be monomeric (one metal center), dimeric (two metal centers) or can have a plurality of metal centers greater than two, such as 3, 4, 5 or more than 5 metal centers. For example, specific examples of suitable hafnium and zirconium precursors include, but are not limited to, HfCl4, HfMe4, Hf(CH2Ph)4, Hf(CH2Ph-p-SiMe3)4, Hf(CH2CMe3)4, Hf(CH2SiMe3)4, Hf(CH2Ph)3Cl, Hf(CH2Ph-p-SiMe3)3Cl, Hf(CH2CMe3)3Cl, Hf(CH2SiMe3)3Cl, Hf(CH2Ph)2Cl2, Hf(CH2CMe3)2Cl2, Hf(CH2SiMe3)2Cl2, Hf(NMe2)4, Hf(NEt2)4, and Hf(N(SiMe3)2)2Cl2; ZrCl4, ZrMe4, Zr(CH2Ph)4 , Zr(CH2Ph-p-SiMe3), Zr(CH2Ph-p-SiMe3)4, Zr(CH2CMe3)4, Zr(CH2SiMe3)4, Zr(CH2Ph)3Cl, Zr(CH2Ph-p-SiMe3)3Cl, Zr(CH2CMe3)3Cl, Zr(CH2SiMe3)3Cl, Zr (CH2Ph)2Cl2, Zr(CH2CMe3)2Cl2, Zr(CH2SiMe3)2Cl2, Zr(NMe2)4, Zr(NEt2)4, Zr(NMe2)2Cl2, Zr(NEt2)2Cl2, Zr(N(SiMe3)2)2Cl2, TiBn4, TiCl4 and Ti(CH2Ph)4. Lewis base adducts of these examples are also suitable for use as metal precursors. For example, ethers, amines, thioethers, and phosphines are suitable for use as Lewis bases. Specific examples include HfCl4(THF)2, HfCl4(SMe2)2, and Hf(CH2Ph)2Cl2(OEt2). The activated metal precursor may be an ionic or zwitterionic compound, such as (M(CH2Ph)3 + )(B(C6F5)4 - ) or (M(CH2Ph)3 + )(PhCH2B(C6F5)3 - ), wherein M is defined above as Hf or Zr.

[0068] In the metal-ligand complex according to formula (I), each X is bound to M by a covalent bond, a coordinate bond, or an ionic bond. When n is 1, X can be a monodentate ligand or a bidentate ligand; when n is 2, each X is an independently selected monodentate ligand and can be the same as or different from the other groups X. Typically, the metal-ligand complex according to formula (I) is electrically neutral as a whole. In some embodiments, the monodentate ligand can be a monoanionic ligand. The net formal oxidation state of the monoanionic ligand is -1. Each monoanionic ligand can independently be a hydride, (C1-C 40 ) hydrocarbon anion, (C1-C 40 ) heteroalkyl carbon anions, halides, nitrates, HC(O)O - 、HC(O)N(H) - 、(C1-C 40 )alkylC(O)O - 、(C1-C 40 )alkylC(O)N((C1-C 20 )alkyl) - 、(C1-C 40 )alkylC(O)N(H) - 、R K R L B - 、R K R L N - 、R K O - 、R K S - 、R K R L P - or R M R K R L Si - , where R K 、R L and R M are each independently hydrogen, (C1-C 40 )alkyl or (C1-C 40 ) heteroalkyl, or R K and R L are put together to form (C2-C 40 )alkylene or (C1-C 20 ) heteroalkylene, and R M is a group as defined above.

[0069] In other embodiments, at least one monodentate ligand X can be a neutral ligand independent of any other ligand X. In a specific embodiment, the neutral ligand is such as R X NR K R L、R K OR L 、R K SR L or R X PR K R L Neutral Lewis bases, where each R X are independently hydrogen, (C1-C 10 )alkyl-Si[(C1-C 10 )alkyl]3 (i.e. -CH2Si(Me)3), (C1-C 40 )alkyl, [(C1-C 10 )alkyl]3Si- or (C1-C 40 ) heteroalkyl, and each R K and R L are independently groups as defined previously.

[0070] Additionally, each X may be a monodentate ligand that is independent of any other ligand. X is halogen, unsubstituted (C1-C 20 )alkyl, unsubstituted (C1-C 20 )alkyl C(O)O- or R K R L N-, where R K and R L Each of which is independently unsubstituted (C1-C 20 In some embodiments, each monodentate ligand X is a chlorine atom, (C1-C 10 )alkyl (e.g., (C1-C6)alkyl or phenyl), unsubstituted (C1-C 10 )alkyl C(O)O- or R K R L N-, where R K and R L Each of which is independently unsubstituted (C1-C 10 )alkyl.

[0071] In some embodiments, X is benzyl, phenyl or chloro. In other embodiments where n is 2 or 3 such that there are at least two groups X, any two groups X can be linked to form a bidentate ligand. In illustrative embodiments comprising a bidentate ligand, the bidentate ligand can be a neutral bidentate ligand. In one embodiment, the neutral bidentate ligand is of formula (R D )2C=C(R D )–C(R D )=C(R D )2 diene, wherein each R Dis independently H, unsubstituted (C1-C6) alkyl, phenyl or naphthyl. In some embodiments, the bidentate ligand is a monoanionic (Lewis base) ligand. In some embodiments, the bidentate ligand is a divalent anionic ligand. The net formal oxidation state of the divalent anionic ligand is -2. In one embodiment, each divalent anionic ligand is independently carbonate, oxalate (i.e. - O2CC(O)O - )、(C2-C 40 )alkylene divalent carbonium ion, (C1-C 40 ) heteroalkylene carbanion, phosphate or sulfate.

[0072] In further embodiments, X is selected from methyl, ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl, trimethylsilylmethyl; phenyl; benzyl; or chloro. In some embodiments, n is 2, and each X is the same. In some cases, at least two X are different from each other. In other embodiments, n is 2, and each X is a different group from the following: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl, trimethylsilylmethyl; phenyl; benzyl; and chloro. In one embodiment, n is 2, and at least two X groups are independently monoanionic monodentate ligands. In specific embodiments, n is 2, and the two X groups are joined to form a bidentate ligand. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-dimethylsilane-1,3-diyl or 1,3-butadiene.

[0073] In the metal-ligand complex of formula (I), each Y is independently O, S, N (C1-C 40 )alkyl or P(C1-C 40 ) alkyl. In some embodiments, each Y is different. For example, one Y is O and another Y is NCH3. In some embodiments, one Y is O and one Y is S. In another embodiment, one Y is S and one Y is N(C1-C 40 ) alkyl (e.g., NCH 3 ). In further embodiments, each Y is the same. In yet another embodiment, each Y is O. In another embodiment, each Y is S.

[0074] In a specific embodiment of the catalyst system, the metal-ligand complex according to formula (I) may include, but is not limited to, a complex having the structure of any one of procatalysts 1-52:

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081] Co-catalyst component

[0082] By any technique known in the art for activating a metal-based catalyst for olefin polymerization, a catalyst system comprising a metal-ligand complex of formula (I) can be made catalytically active. For example, by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst, a cocatalyst according to the metal-ligand complex of formula (I) can be made catalytically active. In addition, the metal-ligand complex according to formula (I) comprises both a neutral primary catalyst form and a catalytic form that may be positively charged due to the loss of a monomeric ionic ligand (such as a benzyl or phenyl group). Suitable activating cocatalysts used herein include alkyl aluminums; polymeric or oligomeric alumoxanes (alumoxanes) (also referred to as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinated, ionic compounds (including the use of such compounds under oxidizing conditions). Suitable activation techniques are bulk electrolysis. One or more combinations of the aforementioned 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 aluminoxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

[0083] The Lewis acid activating cocatalyst comprises a catalyst comprising (C1-C 20 In some embodiments, the Group 13 metal compound is a tri((C1-C 20 ) alkyl) substituted aluminum or tri((C1-C 20 In other embodiments, the Group 13 metal compound is a tri(hydrocarbyl)substituted aluminum, a tri((C1-C 20 )alkyl)-boron compounds, tri((C1-C 10 )alkyl)aluminum, tri((C6-C 18 ) aryl) boron compounds and halogenated (including perhalogenated) derivatives thereof. In other embodiments, the Group 13 metal compound is tri(fluoro-substituted phenyl) borane, tri(pentafluorophenyl) borane. In some embodiments, the activating cocatalyst is tri((C1-C 20) alkyl borate (e.g. trityl tetrafluoroborate) or tris((C1-C 20 )alkyl)ammonium tetra((C1-C 20 ) alkyl) borate (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" means a bis(C1-C 20 )alkyl)4N + 、((C1-C 20 )alkyl)3N(H) + 、((C1-C 20 )alkyl)2N(H)2 + 、(C1-C 20 )alkylN(H)3 + or N(H)4 + nitrogen cations, each of which (C1-C 20 ) The hydrocarbyl groups (when two or more are present) may be the same or different.

[0084] The combination of neutral Lewis acid activating cocatalysts comprises a mixture comprising a tri((C1-C4)alkyl)aluminum and a tri((C6-C 18 In some embodiments, the present invention relates to a method for preparing a neutral Lewis acid complex comprising: preparing a neutral Lewis acid and a polymeric or oligomeric aluminoxane. ...

[0085] The catalyst system comprising the metal-ligand complex of formula (I) can be activated to form an active catalyst composition by combining with one or more cocatalysts (e.g., a cation-forming cocatalyst, a strong Lewis acid, or a combination thereof). Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes (especially methylaluminoxane) and inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, and combinations thereof.

[0086] In some embodiments, one or more of the aforementioned activating co-catalysts may be used in combination with one another. A specific example of a co-catalyst combination is a mixture of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane or ammonium borate with an oligomeric or polymeric aluminoxane compound. The ratio of the total moles of the one or more metal-ligand complexes of formula (I) to the total moles of the one or more activating co-catalysts in the activating co-catalyst is 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments at least 1:1000; and 10:1 or less, and in some other embodiments 1:1 or less. When aluminoxane is used alone as an activating co-catalyst, the moles of aluminoxane employed are preferably at least 100 times the moles of the metal-ligand complex of formula (I). In some other embodiments, when tris(pentafluorophenyl)borane is used alone as the activating co-catalyst, the ratio of the moles of tris(pentafluorophenyl)borane employed to the total moles of the one or more metal-ligand complexes of formula (I) is 0.5: 1 to 10: 1, 1: 1 to 6: 1, or 1: 1 to 5: 1. The remaining activating co-catalyst is typically employed in a molar amount approximately equal to the total moles of the one or more metal-ligand complexes of formula (I).

[0087] Chain shuttling agents

[0088] The term "shuttling agent" refers to a compound or mixture of compounds employed in the compositions of the present disclosure that, under polymerization conditions, is capable of inducing the exchange of polymeric radicals between at least two active catalyst sites of the catalyst contained in the composition. That is, polymer fragments are transferred to and from one or more of the active catalyst sites. In contrast to shuttling agents, "chain transfer agents" cause the termination of polymer chain growth and are equivalent to a one-time transfer of 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 polymeric radical transfer from the active site of catalyst A to the active site of catalyst B via the shuttling agent, and RB-A is the reverse rate of polymeric radical transfer, i.e., the rate of exchange from the active site of catalyst B to the active site of catalyst A via the shuttling agent. The intermediate formed between the shuttling agent and the polymeric radical chain is sufficiently stable that chain termination is relatively rare. In one or more embodiments, less than 90%, less than 75%, less than 50%, or less than 10% of the shuttle-polymerization products are terminated before three distinguishable polymer segments or blocks are obtained. The chain shuttling rate (defined by the time required to transfer a polymer chain from the catalyst site to the chain shuttling agent and then back to the catalyst site) is equal to or faster than the polymer termination rate, even up to 10 times or even 100 times faster than the polymer termination rate. This allows polymer blocks to form on the same time scale as polymer propagation.

[0089] By selecting different combinations of catalysts and various shuttling agents, polymer products having segments with different stereoregularities or regioerrors, different block lengths, or different numbers of such segments or blocks in each copolymer can be prepared. The catalyst can be selected from metal-ligand complexes of formula (I) with different polymerization abilities, and various shuttling agents or reagent mixtures are paired with these catalyst combinations. For example, if the activity of the shuttling agent is low relative to the catalyst polymer chain proliferation rate of one or more of the catalysts, multi-block copolymers and polymer blends with longer block lengths can be obtained. Conversely, if shuttling is very fast relative to polymer chain proliferation, copolymers with more random chain structures and shorter block lengths are obtained. Extremely fast shuttling agents can produce multi-block copolymers with essentially random copolymer properties. By properly selecting both the catalyst mixture and the shuttling agent, relatively pure block copolymers, copolymers containing larger polymer segments or blocks, and / or blends of the aforementioned substances with various homopolymers and / or copolymers can be obtained.

[0090] A suitable composition comprising catalyst A, catalyst B and a chain shuttling agent can be obtained by the following multi-step procedure which is particularly suitable for block differentiation based on tacticity or regio-errors:

[0091] I. One or more addition-polymerizable C3-30 α-olefin monomers are polymerized using a mixture comprising a latent catalyst and a latent chain shuttling agent. This polymerization test is performed using a batch or semi-batch reactor (i.e., without resupply of catalyst or shuttling agent), preferably operating under solution polymerization conditions with a relatively constant monomer concentration, typically using a catalyst to chain shuttling agent molar ratio of 1:5 to 1:500. After a suitable amount of polymer is formed, the reaction is terminated by adding a catalyst poison, and the polymer properties (tacticity and optionally regio-error content) are measured.

[0092] II. The foregoing polymerization and polymer testing were repeated several times for different reaction times to provide a series of polymers with a range of yields and PDI values.

[0093] III. Catalyst / shuttling agent pairs that exhibit significant polymer transfer to and from the shuttling agent are characterized by a polymer series in which the minimum PDI is less than 2.0, more preferably less than 1.5, and most preferably less than 1.3. In addition, if chain shuttling occurs, the Mn of the polymer will increase linearly with increasing conversion. A catalyst and shuttling agent pair is one that gives a polymer Mn as a function of conversion (or polymer yield) with a statistical accuracy (R2) of the fit greater than 0.95, preferably greater than 0.99.

[0094] Steps I-III are then performed for one or more additional pairings of potential catalysts and / or putative shuttling agents.

[0095] In one or more embodiments, a polymer composition according to the present invention comprising catalyst A, catalyst B, and one or more chain shuttling agents is then selected such that each of the two catalysts undergoes chain shuttling with one or more of the chain shuttling agents, and catalyst A has a more selective ability to form stereospecific polymers than catalyst B under the selected reaction conditions. At least one of the chain shuttling agents performs polymer transfer in both the forward and reverse directions with catalysts A and B (as identified in the aforementioned testing). Additionally, the chain shuttling agent preferably does not reduce the catalyst efficiency (measured as weight of polymer produced per unit time per weight of catalyst) of either catalyst by more than 60% (compared to the activity in the absence of the shuttling agent), more preferably does not reduce such catalyst efficiency by more than 20%, and most preferably increases the catalyst efficiency of at least one of the catalysts compared to the catalyst efficiency in the absence of the shuttling agent.

[0096] Alternatively, the catalyst and shuttling agent pair can also be tested by performing a series of polymerization reactions under standard batch reaction conditions and measuring the resulting polymer properties. Suitable shuttling agents are characterized by a decrease in the resulting Mn without significant broadening of the PDI or loss of activity (reduction in yield or rate) as the shuttling agent loading increases.

[0097] The aforementioned tests are readily adaptable to rapid throughput screening techniques using automated reactors and analytical probes and are suitable for forming polymer blocks having different distinguishing properties (syndiotacticity, isotacticity, and optionally regio-error). For example, a number of potential shuttling agent candidates can be pre-identified or synthesized in situ by combining various organometallic compounds with various proton sources and compounds or reaction products added to a polymerization reaction employing an olefin polymerization catalyst composition. Several polymerizations are performed at varying molar ratios of shuttling agent to catalyst. As a minimum, a suitable shuttling agent is one that produces a minimum PDI of less than 5.0 in a variable yield experiment as described above, while not significantly adversely affecting catalyst activity or catalyst efficiency, and preferably improving catalyst activity and efficiency as described above.

[0098] Regardless of the method used to a priori identify the shuttling agent, the term refers to compounds that are capable of preparing the presently identified multi-block copolymers or that are effectively utilized under the polymerization conditions disclosed herein. It is highly desirable that multi-block copolymers formed according to the present invention have an average number of blocks or segments per average chain (defined as the average number of blocks of different compositions divided by the Mn of the polymer) 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.

[0099] Suitable shuttling agents for use herein include Group 1, Group 2, Group 12, or Group 13 metal compounds or complexes containing at least one C1-20 hydrocarbyl group, preferably a hydrocarbyl-substituted aluminum, gallium, or zinc compound containing 1 to 12 carbon atoms in each hydrocarbyl group, and reaction products thereof with a proton source. The hydrocarbyl group is a linear or branched C2-8 alkyl group. In one or more embodiments of the present disclosure, a shuttling agent may be added to the polymerization process. Chain transfer agents may include trialkylaluminum and dialkylzinc compounds, particularly triethylaluminum, tri(isopropyl)aluminum, tri(isobutyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, triethylgallium, or diethylzinc. Other suitable shuttling agents include the reaction products or mixtures formed by combining the aforementioned organometallic compounds, preferably tri(C1-8)alkylaluminum or di(C1-8)alkylzinc compounds, especially triethylaluminum, tri(isopropyl)aluminum, tri(isobutyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, or diethylzinc, with a less than stoichiometric amount (relative to the number of hydrocarbyl groups) of a secondary amine or hydroxyl compound, especially bis(trimethylsilyl)amine, tert-butyl(dimethyl)siloxane, 2-hydroxymethylpyridine, di(n-pentyl)amine, 2,6-di(tert-butyl)phenol, ethyl(1-naphthyl)amine, bis(2,3,6,7-dibenzo-1-azepanamine), or 2,6-diphenylphenol. In some embodiments, the shuttling agent can be selected from an amine or hydroxyl reagent such that one hydrocarbyl group remains per metal atom. The major reaction products of the aforementioned combinations used as shuttling agents in the present disclosure are n-octylaluminum bis(bis(trimethylsilyl)amide), isopropylaluminum bis(dimethyl(tert-butyl)siloxane) and n-octylaluminum bis(pyridyl-2-methoxide), isobutylaluminum bis(dimethyl(tert-butyl)siloxane), isobutylaluminum bis(bis(trimethylsilyl)amide), n-octylaluminum bis(pyridine-2-methoxide), isobutylaluminum bis(di(n-pentyl)amide), n-octylaluminum di(2,6 -di-tert-butylphenolate), n-octylaluminum bis(ethyl(1-naphthyl)amide), ethylaluminum bis(tert-butyldimethylsilicium), ethylaluminum bis(bis(trimethylsilyl)amide), ethylaluminum bis(2,3,6,7-dibenzo-1-azacycloheptylamide), n-octylaluminum bis(2,3,6,7-dibenzo-1-azacycloheptylamide), n-octylaluminum bis(dimethyl(tert-butyl)silicium, ethylzinc(2,6-diphenylphenolate), and ethylzinc(tert-butylcarbamate).

[0100] It will be appreciated by those skilled in the art that a suitable shuttling agent for one catalyst or catalyst combination may not necessarily be equally good or even satisfactory for use with a different catalyst or catalyst combination. Some potential shuttling agents may adversely affect the performance of one or more catalysts and may be precluded from use in the polymerization methods of the present disclosure. Therefore, the activity of the chain shuttling agent should be balanced with the catalytic activity of the catalyst to obtain a polymer having hard and soft segments.

[0101] However, shuttling agents generally have the highest polymer transfer rates and the highest transfer efficiency (reduced incidence of chain termination). Such shuttling agents can be used at reduced concentrations and still achieve a certain degree of shuttling. In addition, such shuttling agents result in the shortest polymer block lengths. Chain shuttling agents with a single exchange site are employed because the effective molecular weight of the polymer in the reactor is reduced.

[0102] polyolefins

[0103] The catalytic system described in the preceding paragraphs is used to polymerize olefins, primarily ethylene and propylene. In some embodiments, only a single type of olefin or α-olefin is present in the polymerization scheme, thereby forming a homopolymer. However, additional α-olefins can be incorporated into the polymerization procedure. Additional α-olefin comonomers typically have no more than 20 carbon atoms. For example, the α-olefin comonomer can have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, the one or more α-olefin comonomers can be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or in an alternative embodiment, selected from the group consisting of 1-hexene and 1-octene.

[0104] In some embodiments, the ethylene-based polymer may include 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 may include 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 in the alternative, 70 to 100 mole percent of units derived from ethylene; 70 to 89.5 mole percent of units derived from ethylene; or 69 to 85.5 mole percent of units derived from ethylene.

[0105] In some embodiments of the ethylene-based polymers, the amount of the additional α-olefin is less than 50 mol%; other embodiments comprise at least 1 mole percent (mol%) to 40 mol%; and in yet other embodiments, the amount of the additional α-olefin comprises at least 10 mol% to 20 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0106] Any conventional polymerization process may be employed to produce ethylene-based polymers. Such conventional polymerization processes include, but are not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof using, for example, one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors in parallel or in series, or any combination thereof.

[0107] In one embodiment, a polymer based on ethylene can be produced in a dual reactor system (for example, a double loop reactor system) by solution polymerization, wherein ethylene and optionally one or more alpha olefins are polymerized in the presence of a catalyst system as described herein and optionally one or more cocatalysts. In another embodiment, a polymer based on ethylene can be produced in a dual reactor system (for example, a double loop reactor system) by solution polymerization, wherein ethylene and optionally one or more alpha olefins are polymerized in the presence of the disclosure and a catalyst system as described herein and optionally one or more other catalysts. Catalyst systems as described herein can optionally be used in combination with one or more other catalysts in the first reactor or the second reactor. In one embodiment, a polymer based on ethylene can be produced in a dual reactor system such as a double loop reactor system via solution polymerization, wherein ethylene and optionally one or more alpha olefins are polymerized in the presence of a catalyst system as described herein in these two reactors.

[0108] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single reactor system (e.g., a single loop reactor system) in which ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system as described within the present disclosure and optionally one or more cocatalysts as described in the preceding paragraphs.

[0109] Ethylene-based polymers can further include one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. Ethylene-based polymers can contain any amount of additives. By the weight of the ethylene-based polymer and one or more additives, the ethylene-based polymer can include about 0 percent to about 10 percent of the total weight of such additives. Ethylene-based polymers can further include fillers, which can include, but are not limited to, organic or inorganic fillers. By the combined weight of the ethylene-based polymer and all additives or fillers, the ethylene-based polymer can contain about 0 to about 20 weight percent fillers, such as, calcium carbonate, talc, or Mg(OH) 2. Ethylene-based polymers can further be blended with one or more polymers to form a blend.

[0110] In some embodiments, a polymerization process for producing an ethylene-based polymer may comprise polymerizing ethylene and at least one additional alpha olefin in the presence of a catalyst system, wherein the catalyst system incorporates at least one metal-ligand complex of formula (I). The density of the polymer produced by such a catalyst system incorporating the metal-ligand complex of formula (I) may be, for example, 0.850 g / cm2 according to ASTM D792 (incorporated herein by reference in its entirety). 3 to 0.950g / cm 3 、0.880g / cm 3 to 0.920g / cm 3 、0.880g / cm 3 to 0.910g / cm 3 , or 0.880g / cm 3 to 0.900g / cm 3 .

[0111] In another embodiment, the melt flow ratio (I) of the polymer produced by the catalyst system comprising the metal-ligand complex of formula (I) is 10 / I2) is 5 to 15, wherein the melt index I2 is measured according to ASTM D1238 (incorporated herein by reference in its entirety) at 190°C and a load of 2.16 kg, and the melt index I 10 Measured according to ASTM D1238 at 190°C and 10 kg load. In other embodiments, the melt flow ratio (I 10 / I2) is 5 to 10, and in other embodiments, the melt flow ratio is 5 to 9.

[0112] In some embodiments, the polymer produced by the catalyst system comprising the metal-ligand complex of formula (I) has a polydispersity index (PDI) of 1 to 25, wherein PDI is defined as M w / M n , M w is the weight average molecular weight and M n is the number average molecular weight. In other embodiments, the polymer produced by the catalyst system has a PDI of 1 to 6. Another embodiment comprises a PDI of 1 to 3; and other embodiments comprise a PDI of 1.5 to 2.5.

[0113]

[0014] Embodiments of the catalyst systems described in this disclosure produce unique polymer properties due to the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

[0114] Unless otherwise noted, all solvents and reagents were purchased from commercial sources and used as received. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passing through activated alumina and, in some cases, through Q-5 reactants. Solvents used for experiments conducted in a nitrogen-filled glove box were obtained by purifying the solvents in an activated alumina solution. The samples were further dried by storage over 4% zeolite. Glassware used for moisture-sensitive reactions was oven-dried 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 to a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separations were performed on an XBridge C18 3.5 μm 2.1 mm × 50 mm column using a gradient of acetonitrile to water from 5:95 to 100:0 using 0.1% formic acid as the ionizer. HRMS analysis was performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8 μm 2.1 mm × 50 mm column coupled to an Agilent 6230 TOF mass spectrometer with electrospray ionization. 1 H NMR data are reported as follows: chemical shift (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, sex = sextet, sept = septet, and m = multiplet), integration, and assignment). Chemical shifts are reported in ppm upfield from internal tetramethylsilane (TMS, scale δ) using residual protons in the deuterated solvent as reference. 1 Chemical shifts of HNMR data were calculated using 1 H decoupling method was used to determine 13 C NMR data, and chemical shifts are reported relative to the upfield from tetramethylsilane (TMS, scale δ) using the protons remaining in the deuterated solvent as reference.

[0115] General procedure for PPR screening experiments

[0116] The polyolefin catalytic screening was 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 in an inert atmosphere glove box. Each cell is equipped with a glass insert with an internal working liquid volume of approximately 5 mL. Each cell has an independent pressure control device, and the liquid in the cell is continuously stirred at a speed of 800 rpm. Unless otherwise stated, the catalyst solution is prepared by dissolving an appropriate amount of the primary catalyst in toluene. All liquids (e.g., solvent, 1-octene, chain shuttling agent solution suitable for the experiment, and catalyst solution) are added to the single-cell reactor by a robotic syringe. Gaseous reagents (i.e., ethylene, H2) are added to the single-cell reactor through a gas injection port. Before each run, the reactor is heated to 80°C, purged with ethylene, and exhausted.

[0117] A portion of Isopar-E was added to the reactor. The reactor was heated to operating temperature and pressurized with ethylene to the appropriate psig. The reagents were added in the following order as toluene solutions: (1) 1-octene with 500 nmol of scavenger MMAO-3A; (2) activator (cocatalyst-1, cocatalyst-2, etc.); and (3) catalyst.

[0118] Each liquid addition was tracked with a small amount of Isopar-E so that after the final addition, a total reaction volume of 5 mL was reached. After the catalyst was added, the PPR software began monitoring the pressure of each cell. The pressure was maintained (within approximately 2-6 psig) by supplementing the addition of ethylene gas by opening the valve at the set point minus 1 psi and closing the valve when the pressure reached 2 psi or more. All pressure drops were accumulated and recorded as "absorption" or "conversion" of ethylene during the run, or until the absorption or conversion requirement was reached, whichever occurred first. Each reaction was quenched for 4 minutes by adding 10% carbon monoxide in argon at 40-50 psi higher than the reactor pressure. A shorter "quenching time" means that the catalyst is more active. To prevent too much polymer from forming in any given cell, the reaction was quenched after reaching a predetermined absorption level (50 psig for 120°C operation and 75 psig for 150°C operation). After all reactions were quenched, the reactor was cooled to 70°C. The reactor was evacuated, purged with nitrogen for 5 minutes to remove carbon monoxide, and the tube was removed. Polymer samples were dried in a centrifugal evaporator at 70°C for 12 hours, weighed to determine polymer yield and analyzed by IR (1-octene incorporation) and GPC (molecular weight).

[0119] SymRAD HT-Compositional GPC Analysis

[0120] Molecular weight data for samples generated from PPR experiments were determined by analysis on a hybrid Symyx / Dow built robotic-assisted dilution high-temperature gel permeation chromatograph (Sym-RAD-GPC). Polymer samples were dissolved in 1,2,4-trichlorobenzene (TCB) at a concentration of 10 mg / mL, stabilized by 300 parts per million (ppm) of butylated hydroxytoluene (BHT), by heating at 160°C for 120 minutes. Each sample was diluted to 1 mg / mL immediately before injection of a 250 μL aliquot. The GPC was equipped with two Polymer Labs PLgel 10 μm MIXED-B columns (300 mm × 10 mm) at a flow rate of 2.0 mL / min at 160°C. Sample detection was performed using a PolymerChar IR5 detector in concentrated mode. Conventional calibration with narrow polystyrene (PS) standards was used, and the apparent units were adjusted to homopolyethylene (PE) at this temperature using the known Mark-Houwink coefficients of PS and PE in TCB. Octene incorporation was determined by using a linear calibration developed by analyzing copolymers of known composition using a PolymerChar IR 5 detector.

[0121] IR analysis of 1-octene incorporation

[0122] Samples for HT-GPC analysis were run prior to IR analysis. In some cases, octene incorporation was determined based on component GPC analysis, while in other cases, separate IR analysis was performed. For IR analysis, samples were deposited and analyzed for 1-octene incorporation using 48-well HT silicon wafers. For the analysis, the samples were heated to 160°C for less than or equal to 210 minutes; the samples were reheated to remove the magnetic GPC stir bar and shaken with a glass stir bar on a J-KEM Scientific heated robotic shaker. The samples were deposited while heating using a Tecan MiniPrep 75 deposition station, and 1,2,4-trichlorobenzene was evaporated from the deposited wafer wells at 160°C under a nitrogen purge. Analysis of 1-octene was performed on HT silicon wafers using a NEXUS 670E SPFT-IR.

[0123] Batch Reactor Polymerization Procedure

[0124] Batch reactor polymerization was carried out in a 2L Parr TM The reactor is heated by an electric heating mantle and cooled by an internal winding cooling coil containing cooling water. TMThe TG process computer controls and monitors the reactor and heating / cooling system. The bottom of the reactor is equipped with a dump valve that empties the reactor contents into a stainless steel dump pot. The dump pot is pre-filled with a catalyst kill solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). The dump pot is discharged into a 30-gallon blowdown tank, and both the pot and the tank are purged with nitrogen. All solvents used for polymerization or catalyst replenishment are run through solvent purification columns to remove any impurities that may affect polymerization. 1-Octene and Isopar E are passed through two columns, the first column containing A2 alumina and the second column containing Q5. Ethylene is passed through two columns, the first column containing A204 alumina and molecular sieves, the second column contains the Q5 reactant. The N2 used for transfer passes through the column containing A204 alumina, A single column of molecular sieves and Q5.

[0125] The reactor is first loaded from a spray tank which may contain Isopar E solvent and / or 1-octene, depending on the reactor load. The spray tank is filled to the load set point using a laboratory scale equipped with a spray tank. After the liquid feed is added, the reactor is heated to the polymerization temperature set point. If ethylene is used, it is added to the reactor when it is at reaction temperature to maintain the reaction pressure set point. The amount of ethylene added is monitored by a micro-motion flow meter. For some experiments, the standard conditions at 120°C were 611 g of Isopar E containing 46 g of ethylene and 303 g of 1-octene, and the standard conditions at 150°C were 547 g of Isopar E containing 43 g of ethylene and 303 g of 1-octene.

[0126] The procatalyst and activator were mixed with an appropriate amount of purified toluene to achieve a molar solution. The procatalyst and activator were handled in an inert glove box, drawn into a syringe, and pressure-transferred into a catalyst injection tank. The syringe was rinsed three times with 5 mL of toluene. A timer was started immediately after the catalyst addition. If ethylene was used, it was added via a Camile to maintain the reaction pressure set point in the reactor. The polymerization reaction was run for 10 minutes, after which the agitator was stopped and the bottom dump valve was opened to empty the reactor contents into a dump pot. The contents of the dump pot were poured into a tray and placed in a laboratory fume hood, where the solvent was evaporated overnight. The tray containing the remaining polymer was transferred to a vacuum oven, where it was heated under vacuum up to 140°C to remove any remaining solvent. After the tray cooled to ambient temperature, the polymer yield was weighed to measure efficiency and submitted for polymer testing.

[0127] PolymerChar HT - Compositional GPC Analysis

[0128] Polymer samples produced by the batch polymerization process were analyzed by high-temperature GPC analysis using a PolymerChar GPC with an infrared detector (IR5) and Agilent's PLgel MIXED-A columns. Decane (10 μL) was added to each sample to serve as an internal flow marker. The sample was first diluted to a concentration of 10 mg / mL in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm butylated hydroxytoluene (BHT) and then dissolved by stirring at 160°C for 120 minutes. Before injection, the sample was further diluted to a concentration of 2 mg / mL by TCB stabilized with BHT. The sample (200 μL) was eluted through a PLgel 20 μm (50 × 7.5 mm) guard column and then through four PLgel 20 μm (300 × 7.5 mm) MIXED-A columns at a flow rate of 1.0 ml / min, and the columns were maintained at 160°C by TCB stabilized with BHT. The total run time was 40 minutes. For molecular weight (MW) calibration, 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 3rd order MW calibration curve, where the apparent units were calculated using the known Mark-Houwink coefficients (α) of PS and PE. sty =0.722, log K sty =-3.993,α eth =0.725, log K eth =-3.391) adjusted to homopolyethylene (PE). Octene incorporation was determined by using a linear calibration developed by analyzing copolymers of known composition.

[0129] Chain shuttling activity

[0130] In addition to the catalyst efficiency or M w In addition to the molecular weight of the polymer produced by a particular catalyst, understanding the chain transfer ability of a new catalyst is a key aspect of Dow's development of a new line of polyolefin catalysts. The chain transfer ability of a catalyst is initially evaluated by conducting campaigns that vary the level of chain transfer agent or shuttling agent (CSA) to observe the decrease in molecular weight and the expected narrowing of the PDI of the shuttling catalyst. The molecular weight of polymers produced by catalysts that have the potential to be good chain transfer agents will be more sensitive to the addition of CSA than the molecular weight of polymers produced by poor shuttling catalysts. The Mayo equation (Equation 1) describes how a chain transfer agent changes from the natural number average chain length in the absence of a chain transfer agent to the molecular weight of a polymer produced by a catalyst that has the potential to be a good chain transfer agent. Reduce the number average chain length Equation 2 defines the chain transfer or chain shuttling constant, Ca, as the ratio of the chain transfer to propagation rate constants. By assuming that the vast majority of chain propagation occurs through ethylene insertion rather than comonomer incorporation, Equation 3 describes the expected m × n for the polymerization. no is the native molecular weight of the catalyst in the absence of a chain shuttling agent, and M n is the molecular weight observed in the case of chain shuttling agents (M n =M no , chain-free shuttling agent).

[0131]

[0132]

[0133]

[0134] [Monomer] = (Mol% C2) x [ethylene] + (Mol% C8) x [octene] Equation 4

[0135] To determine the chain transfer rates of procatalysts 1-7 and 9-52, semi-batch runs were performed using different amounts of chain transfer agent Et2Zn (0, 50, and 200 μmole). All reactions were carried out at 120°C or 150°C using 1.2 equivalents of [HNMe(C 18 H 37 )2][B(C6F5)4] was used as the activator, and the primary catalysts 7, 8, 11, and 12 were premixed with an excess of MMAO-3A (10.0 equivalents) in a 0.005 M solution for 10 minutes before the polymerization experiments were performed. Batch operations were performed at 120°C and 150°C with 11.1 g or 12.1 g of ethylene, 56 g or 57 g of 1-octene, and 528 g or 555 g of Isopar E at 76-136 psi. The catalyst efficiencies and the corresponding M values ​​of the polymers produced are presented in Table 2. w , PDI, and comonomer incorporation. M for each run was calculated using Equation 3 n , where Ca and M are fitted using Microsoft Excel Solver n0 The value of is chosen to minimize the squared deviation between the fitted and experimental molecular weight data for all runs performed with a particular catalyst. Figure 5 Shows M n A graph showing the [CSA] of the primary catalyst 1-52, including a graph showing M n The line of expected dependence of [CSA] from the best-fit value of Ca and the calculated Ca values ​​are presented in Table 3.

[0136] Examples

[0137] Examples 1 to 111 are methods for synthesizing intermediates, ligands, and isolated procatalysts for ligands, and are described in Figure 1-3 One or more features of the present disclosure are illustrated with the help of the following examples:

[0138] Example 1: Synthesis of hydroxythiophene intermediates Figure 2-3 Follow steps 1 and 2 in the .

[0139]

[0140] To a suspension of hydroxythiophene (10.020 grams, 42.267 mmol, 1.00 equiv) in 1,4-dioxane (100 mL) and H2O (450 mL) was added NaOH (50.000 g, 1.250 mol, 29.6 equiv) in one portion under nitrogen. The now pale yellow mixture was fitted with a reflux condenser and placed in a mantle heated to 80°C. After stirring (500 rpm) for 2.5 hours, TLC of the now golden yellow solution indicated complete conversion of the initial thiophene to the lower R f point. The mixture was removed from the hood and allowed to gradually cool to 23 ° C. It was placed in an ice-water bath for 60 minutes and concentrated HCl (125 mL, 37%) was added over 10 minutes. The now white heterogeneous mixture was removed from the ice-water bath and placed in a hood heated to 60 ° C. It was vigorously stirred (1000 rpm) for 5 hours. The now light golden solution was removed from the hood and gradually cooled to 23 ° C. It was diluted with Et2O (100 mL), stirred vigorously for 2 minutes, poured into a separatory funnel, separated, and the organic matter was washed with HCl aqueous solution (2×100 mL, 1N). The residual organic matter was extracted from the aqueous layer using Et2O (2×50 mL), dried over solid Na2SO4, decanted, and Et2O was removed by rotary evaporation to obtain crude bromo-hydroxythiophene as a 1,4-dioxane solution (100 mL). An aliquot was removed, fully concentrated in vacuo, and NMR indicated a pure product in the form of a mixture of tautomers. The material was used in subsequent experiments without concentration or purification.

[0141] A clear, light yellow solution of hydroxythiophene in 1,4-dioxane (100 mL, from above) was diluted with non-anhydrous, non-deoxygenated THF (400 mL), H2O (6 mL) was added, the solution was placed in an ice-water bath, bubbling with nitrogen for 1 hour, placed under a positive nitrogen stream, and then solid lithium hydroxide monohydrate (3.544 g, 84.453 mmol, 2.00 equiv) was added. The mixture became a dark reddish-brown solution and was vigorously stirred (1000 rpm) for 1 hour, and then neat chloromethyl ethyl ether (11.8 mL, 126.80 mmol, 3.00 equiv) was added dropwise via syringe in a rapid manner. After stirring at 0° C. for 2 hours, the dark brown solution was diluted with aqueous NaOH (200 mL, 1 N), stirred for 2 minutes, the THF was removed in vacuo, the biphasic mixture was diluted with CHCl (100 mL), suction filtered through a pad of celite, rinsed with CHCl (4×50 mL), the dark brown filtrate mixture was poured into a separatory funnel, separated, and the organics were washed with aqueous NaOH (2×100 mL, 1 N). The residual organics were extracted from the aqueous solution using CHCl (2×50 mL), combined, dried over solid NaSO, decanted, and carefully concentrated to give a golden brown oil, which was diluted with CHCl (25 mL), suction filtered through a pad of silica gel, rinsed with CHCl (4×50 mL), and the filtrate was concentrated to give the thiophene ether (9.534 g, 40.209 mmol, 95% two steps) as a golden oil. NMR indicated the product.

[0142] The hydroxythiophene product exists as a mixture of keto-enol tautomers: (*) keto tautomer

[0143] 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*), (103.07*), 100.24, (37.05*).

[0144] Characterization of protected hydroxythiophenes:

[0145] 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 C NMR (101 MHz, chloroform-d) δ 151.51, 121.50, 103.84, 101.55, 95.07, 64.53, 15.05.

[0146] Example 2: Synthesis of carbazolethiophene—— Figure 2 Step 4 in

[0147]

[0148] A mixture of bromothiophene (1.034 g, 4.361 mmol, 1.00 equiv), carbazole (1.604 g, 9.594 mmol, 2.20 equiv), Cu2O (1.248 g, 8.722 mmol, 2.00 equiv) and K2CO3 (6.027 g, 43.610 mmol, 10.00 equiv) was evacuated and backfilled with N2. This process was repeated 4 more times. Deoxygenated anhydrous xylene (22 mL) was added via syringe, followed by N,N'-DMEDA (1.90 mL, 17.440 mmol) via syringe. 1, 4.00 equivalents), the mixture was placed in a mantle heated to 140 ° C and stirred (500 rpm) for 72 hours, removed from the mantle, the now dark red-black mixture was gradually cooled to 23 ° C, silica gel was added, the mixture was suction filtered on a silica gel pad, washed with CH2Cl2 (4×30 mL), and the golden brown filtrate was concentrated on celite and purified several times by silica gel chromatography using an ISCO chromatography purification system; using 15% CH2Cl2 in hexanes to give the thiophene-carbazole product (1.006 g, 3.110 mmol, 71%) as a white crystalline solid. Combined fractions were collected and re-purified using the same method.

[0149] 1 H NMR (500 MHz, CHLOROFORM-d) δ 8.12 (dt, J = 7.7, 1.0 Hz, 2H), 7.43–7.38 (m, 3H), 7.31–7.26 (m, 4H), 6.90 (d, J = 3.6 Hz, 1H), 5.04 (s, 2H), 3.53 (q, J = 7.1 Hz, 2H), 1.14 (t, J = 7.0 Hz, 3H). 13C NMR (126 MHz, chloroform- d ) δ 150.82, 141.23, 127.05, 125.77, 123.17, 120.78, 120.14, 119.80, 110.17, 102.44, 94.75, 64.42, 14.99.

[0150] Example 3: Synthesis of Thiophene Boron Pinacolac Figure 2 Step 5 in

[0151]

[0152] A clear, light yellow solution of thiophene (0.410 g, 1.268 mmol, 1.00 equiv) in anhydrous, deoxygenated THF (30 mL) in a nitrogen-filled glove box was placed in a refrigerator cooled to -35°C for 12 hours, and then pre-cooled n-BuLi (0.73 mL, 1.902 mmol, 1.50 equiv, titrated to 2.61 M / hexane) was added dropwise. After 3 hours in the refrigerator, isopropoxyboropinacol (0.52 mL, 2.536 mmol, 2.00 equiv) was added neat via syringe in a rapid dropwise addition. The pale yellow solution turned into a slightly pale yellow mixture, which was removed from the refrigerator and stirred at 23° C. for 2 hours before the white heterogeneous mixture was removed from the glove box, neutralized with aqueous phosphate buffer (50 mL, pH=8, 0.05 M), concentrated to remove THF, diluted with CHCl (20 mL), poured into a separatory funnel, separated, and the organics washed with aqueous phosphate (2×50 mL, pH=8, 0.05 M). The remaining organics were extracted from the aqueous solution using CHCl (2×20 mL), combined, dried over solid NaSO, decanted, and concentrated. The crude yellow mixture was dissolved in CHCl (10 mL), suction filtered through a pad of silica gel, rinsed with CHCl (4×20 mL), and concentrated to give thiopheneboronopinacol (0.560 g, 1.246 mmol, 98%) as an amorphous white foam. NMR indicated the product contained trace impurities including the undesired isomer and the starting i-PrO-BPin. The slightly impure product was used in the subsequent reaction without further purification.

[0153] 1H NMR (400 MHz, CHLOROFORM-d) δ 8.08 (dt, J = 7.8, 1.0 Hz, 2H), 7.65 (s, 1H), 7.38 (ddd, J = 8.2, 7.0, 1.2 Hz, 2H), 7.31 (dt, J = 8.2, 1.0 Hz, 2H), 7.28–7.22 (m, 2H), 4.88 (s, 2H), 2.80 (q, J = 7.1 Hz, 2H), 1.36 (s, 12H), 0.48 (t, J = 7.1 Hz, 3H). 13 CNMR (126 MHz, chloroform-d) δ 159.02, 141.07, 130.52, 127.88, 125.96, 123.07, 119.99, 119.91, 110.45, 98.40, 84.27, 64.43, 24.81, 14.07.

[0154] Example 4: Synthesis of Ligand 1 Figure 2 Step 6 in

[0155]

[0156] To a solution of bisprotected thiophene (55.0 mg, 0.0642 mmol, 1.00 equiv) in 1,4-dioxane / CH2Cl2 (6 mL, 1:2) was added concentrated HCl (4 mL) under nitrogen. The golden brown biphasic solution was stirred vigorously (1000 rpm) for 24 hours, diluted with aqueous HCl (10 mL, 1 N), diluted with CHCl (10 mL), poured into a separatory funnel, separated, and the organics washed with aqueous HCl (2×10 mL, 1 N). The remaining organics were extracted from the aqueous layer with CHCl (2×10 mL), combined, dried over solid NaSO, decanted, and concentrated. Residual dioxane was azeotropically removed using PhMe (4×5 mL). The resulting dark brown amorphous foam was dissolved in CHCl (5 mL) and suction filtered onto a pad of silica gel, rinsed with CHCl (4×20 mL), and the resulting golden filtrate solution was concentrated to provide the diol (44.5 mg, 0.0601 mmol, 94%) as an amorphous golden brown foam. NMR indicated pure product.

[0157] 1 H NMR (500 MHz, CHLOROFORM-d) δ 8.12 (d, J = 7.8 Hz, 4H), 7.61 (dd, J = 7.6, 1.7 Hz, 2H), 7.40–7.12 (m, 16H), 6.99 (s, 2H), 6.87 (d, J = 8.3 Hz, 2H), 4.02 (d, J = 5.1 Hz, 4H), 1.87 (q, J = 2.9 Hz, 4H). 13C NMR (126 MHz, chloroform-d) δ 153.65, 146.41, 141.19, 130.45, 129.02, 128.82, 128.22, 127.08, 125.77, 125.51, 123.22, 123.03, 120.73, 120.20, 119.85, 114.10, 110.19, 69.86, 30.32. HRMS (ESI): [M+Na] + Calculated as 791.2008; actual value is 791.2012.

[0158] Example 5: Synthesis of Main Catalyst 1

[0159]

[0160] Before use, the thiophene ligand was azeotropically dried using PhMe (4 x 10 mL). To a suspension of thiophene L-1 (6.5 mg, 0.00850 mmol, 1.00 equiv) in d-PhMe (1.50 mL) in a nitrogen-filled glove box at 23°C was added a solution of ZrBn4 (3.9 mg, 0.00850 mmol, 1.00 equiv) in d-PhMe (0.16 mL) dropwise. After stirring (500 rpm) for 1 hour, the golden yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.005 M d-PhMe solution. NMR indicated the product.

[0161] 1 H NMR (400 MHz, toluene-d8) δ 8.17–8.10 (m, 2H), 7.83 (dt, J = 7.7, 1.0 Hz, 2H), 7.34–7.20 (m, 12H), 7.14–6.95 (m, 2H), 6.93 (ddd, J = 9.2, 7.5, 1.8 Hz, 4H), 6.81 (s, 2H), 6.80–6.68 (m, 6H), 6.06–5.9 9(m,4H),4.93(dd,J=8.2,1.3Hz,2H),3.92(t,J=10.7Hz,2H),3.24(dd,J=12.0,4.7Hz,2H),0 .91(d,J=12.3Hz,2H), 0.81(t,J=9.4Hz,2H), 0.64(t,J=11.4Hz,2H), 0.43(d,J=12.3Hz,2H). 13CNMR (101 MHz, toluene-d8) δ 155.86, 152.25, 146.57, 140.83, 140.75, 130.80, 128.87, 126.96, 126.42, 125.81, 124.54, 123.40, 122.35, 120.69, 120.38, 120.31, 119.79, 119.63, 117.78, 117.02, 112.53, 109.07, 80.70, 74.68, 25.86.

[0162] Example 6: Synthesis of Primary Catalyst 2

[0163]

[0164] To a suspension of ligand L-1 (8.1 mg, 10.53 μmol, 1.00 equivalent) in anhydrous C6D6 (1.0 mL) in a nitrogen-filled glove box at 23 ° C, a solution of HfBn4 (5.7 mg, 10.53 μmmol, 1.00 equivalent) in C6D6 (0.30 mL) was slowly added dropwise. After the addition was complete, the initial mixture was converted into a transparent light yellow solution. After stirring (500 rpm) for 20 minutes at 23 ° C, NMR indicated that the initial ligand was completely consumed. The light yellow solution was filtered through a 0.20 μm PTFE filter, rinsed with anhydrous deoxygenated PhMe (3 × 3 mL), and the filtrate was concentrated to give a hafnium complex (11.1 mg, 9.840 μmol, 93%) as an off-white powder. NMR indicated pure product.

[0165] 1 H NMR (400MHz, benzene-d6) δ8.16–8.07(m,2H),7.82(dt,J=7.7,1.0Hz,2H),7.33–7.27(m,2H),7.27–7.2 0(m,6H),7.20–7.15(m,4H),7.02(ddd,J=7.9,7.1,1.0Hz,2H),7.00–6.93(m,4H),6.74(s,2H),6. 73–6.65(m,6H),6.13–6.06(m,4H),4.95–4.89(m,2H),3.93–3.84(m,2H),3.20(dd,J=11.9,4.7H z,2H),0.84(d,J=13.3Hz,2H),0.71–0.62(m,2H),0.39(d,J=12.0Hz,2H),0.19(d,J=13.3Hz,2H). 13C NMR (101 MHz, benzene-d6) δ 155.54, 152.27, 147.45, 140.79, 140.66, 130.77, 129.59, 128.03, 127.13, 127.07, 126.67, 126.10, 124.95, 124.53, 123.67, 122.27, 120.79, 120.46, 120.35, 119.80, 119.70, 117.92, 116.45, 112.57, 109.14, 81.71, 78.29, 25.98.

[0166] Example 7: Synthesis of Primary Catalyst 7

[0167]

[0168] Prior to use, the thiophene ligand was azeotropically dried using PhMe (4 x 10 mL). To a suspension of thiophene (13.0 mg, 0.0169 mmol, 1.00 equiv) in anhydrous deoxygenated PhMe (3.0 mL) in a nitrogen-filled glove box at 23°C was added dropwise a solution of ZrBnCl(OEt) (7.8 mg, 0.0186 mmol, 1.10 equiv) in PhMe (0.34 mL). After stirring (500 rpm) for 45 minutes, the now golden-yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.005 M PhMe solution, which was used directly in polymerization experiments. The complex solution was concentrated to obtain the solid dichloride complex (15.0 mg, 0.0167 mmol, 99%) free of EtO.

[0169] 1 H NMR (500MHz, benzene-d6) δ8.18–8.11(m,2H),8.04(dt,J=7.7,1.0Hz,2H),7.28–7.13(m,8H),7.11–7.07(m,4H),7.03–6.87(m,4H), 6.74(s,2H),6.70–6.62(m,4H),5.31–5.24(m,2H),4.04(s,2H),3.11–3.01(m,2H),0.72–0.64(m,2H),0.48(d,J=11.9Hz,2H).

[0170] Example 8: Synthesis of Primary Catalyst 8

[0171]

[0172] Before use, thiophene ligand L-1 was dried using PhMe (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (2.07 mL) white suspension of thiophene (8.9 mg, 0.01157 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added HfBn2Cl2(OEt2) (5.9 mg, 0.01157 mmol, 1.00 equivalent) C6D6 (0.24 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.005 M C6D6 solution. NMR indicated the product containing Et2O (1.00 equivalent). The same procedure can be used to prepare a primary catalyst solution directly used in polymerization experiments after filtration using PhMe.

[0173] 1 H NMR (500MHz, benzene-d6) δ8.15–8.13(m,2H),8.04(ddd,J=7.7,1.3,0.8Hz,2H),7.27–7.23(m,3H),7.23–7.19(m,5H),7.19–7.14(m,4H),6.77(s,2 H), 6.68–6.62 (m, 4H), 5.27 (dd, J = 7.6, 2.0Hz, 2H), 4.14 (t, J = 10.8Hz, 2H), 3.17–3.09 (m, 2H), 0.69 (t, J = 9.7Hz, 2H), 0.44 (d, J = 12.1Hz, 2H). 13 C NMR (126 MHz, benzene-d6) δ 152.08, 140.91, 140.71, 129.90, 129.52, 128.27, 126.74, 126.11, 124.82, 124.65, 124.21, 124.18, 122.11, 120.76, 120.23, 119.88, 119.38, 118.29, 117.09, 112.64, 112.54, 108.96, 84.28, 31.95.

[0174] Example 9: Synthesis of the precursor of ligand 2

[0175]

[0176] A mixture of Pd(AmPhos)2Cl2 (60.0 mg, 0.0844 mmol, 0.10 equiv), thiophene bromide (200.0 mg, 0.8436 mmol, 1.00 equiv), boronic acid (208.0 mg, 1.265 mmol, 1.50 equiv) and K3PO4 (804.0 mg, 3.796 mmol, 4.50 equiv) in a vial equipped with a stir bar was evacuated and then backfilled with nitrogen. This evacuation / backfill process was repeated four more times, and then freshly deoxygenated 1,4-dioxane (10.0 mL) and freshly deoxygenated water (1.0 mL) were added sequentially. The vial was capped under a positive N2 flow and placed on a heating plate. The mixture was stirred at 50°C in a hood and the magenta solution was stirred (500 rpm) for 24 hours. The mixture was removed from the hood and the now dark purple solution was cooled to 23°C, diluted with CHCl (10 mL), suction filtered through a pad of silica gel, rinsed with CHCl (4 x 20 mL), and the resulting filtrate was concentrated. Residual 1,4-dioxane was azeotroped with PhMe (4 x 5 mL). The resulting dark purple foam was dissolved in CHCl (10 mL), concentrated onto Celite, and purified by silica gel chromatography; 5% to 25% CHCl in hexanes to give mesitylene-thiophene (155.0 mg, 0.5608 mmol, 66%) as a clear, colorless oil. NMR indicated pure product.

[0177] 1 H NMR (500 MHz, CHLOROFORM-d) δ 6.95 (s, 2H), 6.91 (d, J = 3.4 Hz, 1H), 6.74 (d, J = 3.4 Hz, 1H), 5.11 (s, 2H), 3.63 (q, J = 7.1 Hz, 2H), 2.33 (s, 3H), 2.09 (s, 6H), 1.21 (t, J = 7.1 Hz, 3H). 13 CNMR (126 MHz, chloroform-d) δ 153.05, 137.51, 137.14, 132.90, 131.48, 127.93, 121.39, 101.08, 94.52, 64.03, 21.14, 20.40, 20.39, 15.13.

[0178] Example 10: Synthesis of the precursor of ligand 2

[0179]

[0180] A clear, light yellow solution of thiophene (0.410 g, 1.268 mmol, 1.00 equiv) in anhydrous, deoxygenated THF (30 mL) in a nitrogen-filled glove box was placed in a refrigerator cooled to -35°C for 12 hours, and then pre-cooled n-BuLi (0.73 mL, 1.902 mmol, 1.50 equiv, titrated to 2.61 M / hexane) was added dropwise. After 3 hours in the refrigerator, isopropoxyboropinacol (0.52 mL, 2.536 mmol, 2.00 equiv) was added neat via syringe in a rapid dropwise addition. The pale yellow solution turned into a slightly pale yellow mixture, which was removed from the refrigerator and stirred at 23° C. for 2 hours before the white heterogeneous mixture was removed from the glove box, neutralized with aqueous phosphate buffer (50 mL, pH=8, 0.05 M), concentrated to remove THF, diluted with CHCl (20 mL), poured into a separatory funnel, separated, and the organics washed with aqueous phosphate (2×50 mL, pH=8, 0.05 M). The remaining organics were extracted from the aqueous solution using CHCl (2×20 mL), combined, dried over solid NaSO, decanted, and concentrated. The crude yellow mixture was dissolved in CHCl (10 mL), suction filtered through a pad of silica gel, rinsed with CHCl (4×20 mL), and concentrated to give thiopheneboronopinacol (0.560 g, 1.246 mmol, 98%) as an amorphous white foam. NMR indicated the product contained trace impurities including the undesired isomer and the starting i-PrO-BPin. The slightly impure product was used in the subsequent reaction without further purification.

[0181] 1 H NMR (500 MHz, chloroform-d) δ 7.21 (s, 1H), 6.92–6.89 (m, 2H), 4.98 (s, 2H), 3.22 (q, J = 7.1 Hz, 2H), 2.31 (s, 3H), 2.09 (s, 6H), 1.36 (s, 12H), 0.96 (t, J = 7.1 Hz, 3H). 13 C NMR (126 MHz, chloroform- d ) δ 161.36, 137.50, 136.96, 136.42, 131.63, 129.13, 127.82, 98.05, 83.84, 64.26, 24.80, 21.04, 20.59, 14.76.

[0182] Example 11: Synthesis of Ligand 2

[0183]

[0184] To a vial equipped with a stir bar was added mesityleneboropinacol (0.293 g, 0.7281 mmol, 2.50 equiv), K 3 PO 4 (0.464 g, 2.184 mmol, 7.50 equiv), Pd (AmPhos) Cl 2 (41.0 mg, 0.0583 mmol, 0.20 equiv), and bisphenyliodonium (0.144 g, 0.2913 mmol, 1.00 equiv). The mixture was evacuated and then backfilled with nitrogen three more times, followed by the sequential addition of deoxygenated 1,4-dioxane (14 mL) and water (1.4 mL) via syringe. The vial was sealed with a PTFE cap under a nitrogen purge stream and then placed in a hood heated to 50°C. After stirring (1000rpm) for 36 hours, the purple-black mixture was removed from the cover, gradually cooled to 23°C, filtered with suction on a silica gel pad, washed with CH2Cl2 (4×20mL), and the transparent purple filtrate was concentrated onto diatomaceous earth and purified by silica gel chromatography using ISCO; 10%-100% CH2Cl2 in hexane gave an impure product, which was purified a second time by silica gel chromatography using ISCO; 25%-80% CH2Cl2 in hexane gave protected coupled mesitylene thiophene (0.218g, 0.2756mmol, 95%) as a light brown foam. NMR indicated a product containing a small amount of impurities, and the mixture was used for subsequent reactions without further purification.

[0185] To the impure protected bithiophene in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL). The dark golden brown solution was stirred vigorously (1000 rpm) at 23°C under nitrogen for 24 hours, then diluted with aqueous HCl (25 mL, 1 N) and CHCl (20 mL). The biphasic mixture was poured into a separatory funnel and separated. The organics were washed with aqueous HCl (2 x 20 mL, 1 N). The remaining organics were extracted from the aqueous layer with CHCl (2 x 10 mL). The combined organics were dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO; 25% to 100% CHCl in hexane to afford the bishydroxythiophene ligand (0.150 g, 0.2223 mmol, 81%, 77% over two steps) as a white foam. NMR indicated pure product.

[0186] 1H NMR (500MHz, chloroform-d) δ7.57(dd,J=7.7,1.7Hz,2H),7.25(d,J=6.9Hz,2H),7.23(s,2H),7.13–7.08(m,2H),6.97(d,J=8. 2Hz, 2H), 6.93 (d, J = 6.0Hz, 4H), 6.93 (s, 2H), 4.10 (d, J = 5.2Hz, 4H), 2.31 (s, 6H), 2.10 (s, 12H), 1.91 (q, J = 2.9Hz, 4H). 13 C NMR (126 MHz, chloroform-d) δ 153.58, 148.41, 137.42, 137.26, 133.66, 131.68, 130.95, 128.12, 128.03, 123.79, 122.98, 121.46, 114.49, 114.34, 69.81, 25.66, 21.11, 20.37.

[0187] Characterization of protected ligands:

[0188] 1 H NMR (500MHz, chloroform-d) δ7.78(dd,J=7.6,1.8Hz,2H),7.28–7.23(m,2H),6.99(td,J=7.5,1.1Hz,2H),6.95(dd,J=8.3,1.1Hz,2H),6.92(d,J=6 .7Hz,6H),4.55(s,4H),4.08(q,J=2.9Hz,4H),3.02(q,J=7.0Hz,4H),2.31(s,6H),2.18(s,12H),2.07–2.01(m,4H),0.81(t,J=7.1Hz,6H). 13 C NMR (126 MHz, chloroform-d) δ 155.90, 149.49, 137.43, 136.89, 134.68, 132.21, 131.23, 128.62, 127.90, 123.24, 122.22, 120.76, 120.40, 112.13, 96.64, 68.13, 64.31, 26.06, 21.05, 20.61, 14.64.

[0189] Example 12: Synthesis of Primary Catalyst 3

[0190]

[0191] At 23 ° C, ZrBn4 (6.7 mg, 0.0147 mmol, 1.00 equivalent) was slowly added dropwise to an anhydrous deoxygenated C6D6 (2.66 mL) suspension of the ligand (9.9 mg, 0.0147 mmol, 1.00 equivalent) in a nitrogen-filled glove box. C6D6 (0.27 mL) solution was added. After the addition was complete, the initial mixture was converted into a transparent light yellow solution. After stirring (500 rpm) for 20 minutes at 23 ° C, NMR indicated that the initial ligand was completely consumed. The golden solution was filtered through a 0.20 μm PTFE filter to obtain a zirconium complex in a 0.005 M golden solution that can be directly used in polymerization experiments. NMR indicated the product. The same experiment can also be performed using PhMe to obtain a catalyst solution suitable for direct use in polymerization experiments.

[0192] 1 H NMR(500MHz, benzene-d6)δ7.44–7.41(m,2H),6.99–6.95(m,2H),6.94(s,2H),6.9 2–6.80(m,10H),6.65(s,2H),6.40–6.37(m,2H),6.28–6.24(m,4H),4.18(t, J=10.2Hz,2H),3.51(d,J=11.3Hz,2H),2.26(s,6H),2.18(s,6H),2.16(s,6H ), 1.99 (d, J = 11.4Hz, 2H), 1.59 (d, J = 11.4Hz, 2H), 0.92 (m, 2H), 0.81 (m, 2H). 13 C NMR (126 MHz, benzene-d6) δ 155.63, 155.47, 146.30, 139.56, 136.81, 134.04, 132.07, 131.70, 129.00, 128.55, 128.31, 128.09, 126.69, 125.84, 122.92, 121.02, 120.70, 116.78, 79.36, 72.04, 25.68, 20.75, 20.63.

[0193] Example 13: Synthesis of Primary Catalyst 4

[0194]

[0195] To a suspension of anhydrous deoxygenated PhMe (2.0 mL) of the ligand (11.6 mg, 0.0172 mmol, 1.00 equiv) in a nitrogen-filled glove box was slowly added a solution of HfBn4 (9.8 mg, 0.0181 mmol, 1.05 equiv) in PhMe (0.39 mL) at 23 ° C. After the addition was complete, the initial mixture was converted into a transparent light yellow solution. After stirring (500 rpm) at 23 ° C. for 20 minutes, NMR indicated that the initial ligand was completely consumed. The light yellow solution was filtered through a 0.45 μm PTFE filter, rinsed with anhydrous deoxygenated de-PhMe (3×3 mL), and the filtrate was concentrated to give a hafnium complex (17.5 mg, 0.0169 mmol, 98%) as an off-white powder. NMR indicated a product containing residual PhMe and HfBn4.

[0196] 1 H NMR (500MHz, benzene-d6) δ7.47–7.43(m,2H),6.97(td,J=7.7,1.7Hz,4H),6.94(s,2H),6.88–6.84(m,6H),6. 70(ddt,J=8.7,7.3,1.4Hz,2H),6.66(s,2H),6.51–6.48(m,1H),6.43(d,J=8.0Hz,1H),6.35(dt,J=8.3, 1.6Hz,2H),6.32–6.29(m,2H),4.20(t,J=10.7Hz,2H),3.59–3.52(m,2H),2.22(s,6H),2.18(s,6H),2.1 0 (s, 6H), 2.07 (d, J = 12.9Hz, 2H), 1.33 (d, J = 12.9Hz, 2H), 0.88 (d, J = 9.9Hz, 2H), 0.66 (d, J = 13.1Hz, 2H). 13 C NMR (126 MHz, benzene-d6) δ 155.71, 155.28, 147.75, 139.93, 136.72, 135.11, 134.20, 131.70, 131.46, 129.87, 129.11, 128.61, 128.56, 128.50, 128.17, 127.30, 126.73, 126.32, 124.02, 121.08, 120.84, 116.20, 81.21, 78.13, 26.10, 21.04, 20.76, 20.33.

[0197] Example 14: Synthesis of the Precursor of Ligand 3

[0198]

[0199] A solid mixture of thiophene (200.0 mg, 0.8436 mmol, 1.00 equiv, from Example 1), boronate (400.0 mg, 1.265 mmol, 1.50 equiv, the product of Example 27 below), K 3 PO 4 (804.0 mg, 3.796, 4.50 equiv) and Pd(AmPhos)Cl 2 (60.0 mg, 0.0844 mmol, 0.10 equiv) in a vial equipped with a stir bar was evacuated and then backfilled with nitrogen four more times before deoxygenated 1,4-dioxane (10.0 mL) and deoxygenated water (1.0 mL) were added sequentially via syringe. The vial was sealed with a PTFE cap under a nitrogen purge stream and placed in a hood heated to 50° C. After vigorous stirring (1000 rpm) for 24 hours, the dark red-black mixture was removed from the hood, gradually cooled to 23° C., diluted with CHCl (20 mL), and filtered with suction on silica gel using CHCl as the eluent. The golden-orange filtrate was concentrated onto celite and purified by silica gel chromatography using an ISCO chromatography purification system; 10%-25% CHCl in hexanes to give 3,5-di-tert-butylphenylthiophene (217.0 mg, 0.6262 mmol, 74%) as an off-white foam. NMR indicated pure product.

[0200] 1 H NMR (500 MHz, CHLOROFORM-d) δ 7.53 (d, J = 2.0 Hz, 2H), 7.48 (d, J = 1.9 Hz, 1H), 7.30 (d, J = 3.5 Hz, 1H), 6.75 (d, J = 3.4 Hz, 1H), 5.27 (s, 2H), 3.82 (q, J = 7.1 Hz, 2H), 1.44 (s, 18H), 1.31 (t, J = 7.1 Hz, 3H). 13 C NMR (126 MHz, chloroform- d ) δ 152.66, 150.49, 135.02, 133.94, 122.58, 121.30, 121.10, 101.68, 94.88, 64.41, 34.95, 31.58, 15.16.

[0201] Example 15: Synthesis of the Precursor of Ligand 3

[0202]

[0203] Before use, thiophene is dried using PhMe (4 × 10 mL) azeotropic drying. Deoxygenated anhydrous THF (10 mL) solution of thiophene (188.0 mg, 0.6262 mmol, 1.00 equivalent) in a nitrogen-filled glove box is placed in a refrigerator cooled to -35 ° C for 12 hours, followed by the dropwise addition of precooled n-BuLi solution (0.38 mL, 0.9393 mmol, 1.50 equivalents, titration 2.5 M / hexane) by a syringe. The solution, now golden orange, is allowed to stand in a refrigerator for 3 hours, which is then removed and, while stirring (500 rpm), pure i-PrOBPin (0.22 mL, 1.065 mmol, 1.70 equivalents) is added dropwise. After stirring at 23° C. for 2 hours, the now pale yellow heterogeneous mixture was removed from the glove box, neutralized with aqueous NaHCO₃ (20 mL), diluted with CHCl₂ (20 mL) and brine (20 mL), poured into a separatory funnel, separated, and the organics washed with a saturated aqueous mixture of NaHCO₃ and brine (2×30 mL, 1:1). The residual organics were extracted from the aqueous layer with CHCl₂ (2×10 mL), combined, dried over solid Na₂SO₄, decanted, concentrated, and diluted with CHCl₂. The golden yellow mixture was suction filtered onto silica gel, washed with CHCl₂ (4×25 mL), and concentrated to afford the thiophene boronate (0.246 g, 0.5206 mmol, 83%) as an off-white solid. NMR indicated the product.

[0204] 1 H NMR (500MHz, chloroform-d) δ7.53(d,J=1.1Hz,1H),7.45(d,J=1.8Hz,2H),7.40(q,J=1.5Hz,1H),5.11(d,J =1.0Hz,2H),3.39(qd,J=7.1,0.9Hz,2H),1.38(s,12H),1.37(s,18H),0.83(td,J=7.1,1.0Hz,3H). 13 C NMR (126 MHz, chloroform- d ) δ 161.11, 150.55, 138.93, 134.08, 128.93, 122.87, 122.51, 121.07, 99.17, 83.94, 64.75, 34.90, 31.51, 24.77, 14.61.

[0205] Example 16: Synthesis of Ligand 3

[0206]

[0207] A mixture of Pd(AmPhos)Cl2 (16.4 mg, 0.0231 mmol, 0.20 equiv, product of Example 4), thiopheneboropinacolate (140.0 mg, 0.3116 mmol, 2.70 equiv, product of Example 5), bisiodophenyl ether (54.0 mg, 0.1154 mmol, 1.00 equiv) and K3PO4 (198.0 mg, 0.9347 mmol, 8.10 equiv) in a vial equipped with a stir bar was evacuated and then backfilled with nitrogen. This evacuation / backfilling process was repeated four more times, and then freshly deoxygenated 1,4-dioxane (5.6 mL) and freshly deoxygenated water (0.56 mL) were added sequentially. The vial was stirred under a positive N2 flow. The mixture was capped and placed in a mantle heated to 50°C. The magenta solution was stirred (500 rpm) for 12 hours, removed from the mantle, and the now dark purple solution was cooled to 23°C, diluted with CHCl (10 mL), filtered with suction on a silica gel pad, rinsed with CHCl (4×20 mL), and the resulting filtrate was concentrated. Residual 1,4-dioxane was removed by azeotropy with PhMe (4×5 mL). The resulting dark purple foam was dissolved in CHCl (10 mL), concentrated onto celite, and purified by silica gel chromatography; 20%-100% CHCl in hexane, and then purified a second time using 60% CHCl in hexane to give the biscoupled thiophene as an off-white amorphous foam. The material was used for subsequent deprotection without further purification. The two-step reaction provided the bishydroxythiophene ligand (72.0 mg, 0.0883 mmol, 43% two steps) as a transparent light golden brown amorphous foam.

[0208] 1 H NMR (500MHz, chloroform-d) δ7.54(tq,J=3.2,1.7Hz,6H),7.48(d,J=2.2Hz,2H),7.43(p,J=1.8,1.3Hz,2H),7.30–7.16(m, 4H), 7.10 (t, J = 7.5Hz, 2H), 6.94 (d, J = 8.2Hz, 2H), 4.16 (d, J = 5.6Hz, 4H), 2.02 (p, J = 3.6, 3.1Hz, 4H), 1.38 (s, 36H). 13 C NMR (126 MHz, chloroform-d) δ 153.67, 150.50, 148.24, 135.49, 134.35, 131.14, 129.04, 128.34, 125.53, 123.64, 122.92, 122.40, 121.29, 120.96, 115.32, 114.37, 69.97, 34.92, 31.53, 25.80.

[0209] Characterization of protected ligands:

[0210] 1 H NMR (500MHz, chloroform-d) δ7.82(dd,J=7.7,1.8Hz,2H),7.49(dd,J=1.9,0.6Hz,4H),7.38(t,J=1.8Hz,2H),7.27–7.23(m,4H),7.00(td,J=7.5,1.0Hz,2H), 6.94(dd,J=8.3,1.1Hz,2H),4.66(s,4H),4.12(d,J=5.2Hz,4H),3.16(q,J =7.0Hz,4H),2.15–2.09(m,4H),1.37(d,J=0.7Hz,36H),0.76–0.69(m,6H). 13 CNMR (126 MHz, chloroform-d) δ 155.89, 150.55, 149.17, 136.79, 134.62, 131.46, 128.72, 124.29, 122.51, 122.04, 120.94, 120.45, 120.40, 112.10, 97.17, 68.07, 64.68, 34.90, 31.52, 26.04, 14.53.

[0211] Example 17: Synthesis of Primary Catalyst 5

[0212]

[0213] Before use, the thiophene ligand was dried using PhMe (4 × 10 mL) azeotropic drying. At 23 ° C, a transparent colorless solution of anhydrous deoxygenated C6D6 (1.63 mL) of thiophene (7.3 mg, 0.0090 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.17 mL) solution of ZrBn4 (4.3 mg, 0.0090 mmol, 1.00 equivalent). After stirring (500 rpm) for 1 hour, an aliquot was removed from the light golden solution, then filtered using a 0.20 μm PTFE submicron filter, rinsed with PhMe (3 × 2 mL), and the transparent light golden filtrate was concentrated to give a zirconium complex (9.5 mg, 0.00831 mmol, 92%) as a light golden foam. NMR indicated product.

[0214] 1H NMR(500MHz, benzene-d6)δ7.61(t,J=1.8Hz,2H),7.59(d,J=1.8Hz,4H),7.40–7.37(m,2H),7.04–7 .00(m,4H),6.87(s,2H),6.87–6.80(m,4H),6.74(tt,J=7.2,1.2Hz,2H),6.62–6.57(m,4H),5 .86–5.83(m,2H),4.18(dd,J=11.9,9.9Hz,2H),3.49(dd,J=12.0,4.9Hz,2H),2.60(d,J=12.0 Hz, 2H), 1.67 (d, J = 12.0Hz, 2H), 1.35 (s, 36H), 0.77 (t, J = 9.4Hz, 2H), 0.43 (d, J = 11.7Hz, 2H). 13 C NMR (126 MHz, benzene-d6) δ 156.38, 155.01, 150.85, 147.58, 137.32, 135.57, 131.38, 129.14, 128.91, 128.47, 128.14, 126.09, 123.64, 123.22, 122.08, 121.03, 119.79, 116.54, 81.38, 76.58, 34.71, 31.40, 26.85.

[0215] Example 18: Synthesis of Primary Catalyst 6

[0216]

[0217] To a suspension of ligand L-3 (8.1 mg, 10.53 μmol, 1.00 equivalent) in a C6D6 aqueous solution (1.0 mL) in a nitrogen-filled glove box at 23 ° C., a C6D6 (0.30 mL) solution of HfBn4 (5.7 mg, 10.53 μmmol, 1.00 equivalent) was slowly added dropwise. After the addition was complete, the initial mixture was converted into a transparent light yellow solution. After stirring (500 rpm) for 20 minutes at 23 ° C., NMR indicated that the initial ligand was completely consumed. The light yellow solution was filtered through a 0.20 μm PTFE filter, rinsed with anhydrous deoxygenated PhMe (3 × 3 mL), and the filtrate was concentrated to give a hafnium complex (11.1 mg, 9.840 μmol, 93%) as an off-white powder. NMR indicated pure product.

[0218] 1H NMR (500MHz, benzene-d6) δ7.62(q,J=1.8Hz,2H),7.55(d,J=1.9Hz,4H),7.38(dt,J=7.6,2.0Hz,2H),7. 06–7.02(m,4H),6.89–6.80(m,4H),6.87(s,2H),6.72(ddd,J=8.8,6.9,1.5Hz,2H),6.59(dt,J=8. 6,1.8Hz,4H),5.86(dd,J=8.0,1.5Hz,2H),4.28(t,J=10.7Hz,2H),3.60–3.53(m,2H),2.37(d,J= 12.8Hz, 2H), 1.45 (d, J = 12.7Hz, 2H), 1.35 (s, 36H), 0.78 (t, J = 9.8Hz, 2H), 0.38 (d, J = 12.0Hz, 2H). 13 C NMR (126 MHz, benzene-d6) δ 156.20, 154.97, 150.83, 147.85, 137.74, 135.51, 131.37, 129.10, 128.91, 128.50, 128.15, 126.67, 126.38, 125.28, 123.79, 123.25, 122.07, 121.19, 119.84, 116.00, 82.15, 80.04, 34.71, 31.40, 31.25, 27.01.

[0219] Example 19: Synthesis of the Precursor of Ligand 4

[0220]

[0221] Before use, bromothiophene was azeotropically dried with toluene (4 x 10 mL). In a nitrogen-filled glove box, a flask equipped with a stir bar was charged with bromothiophene (7.411 g, 31.255 mmol, 1.00 equiv), KOAc (9.203 g, 93.766 mmol, 3.00 equiv), Pd(dppf)Cl2 (1.276 g, 1.563 mmol, 0.05 equiv), and B2Pin2 (8.731 g, 34.381 mmol, 1.10 equiv), and the solid mixture was then suspended in deoxygenated anhydrous 1,4-dioxane (250 mL). The flask was then placed in a mantle heated to 100°C. After stirring (1000 rpm) for 36 hours, the black mixture was removed from the hood, allowed to gradually cool to 23°C, suction filtered onto a pad of silica gel, washed with CHCl (4×20 mL), and the clear dark gray / black filtrate was concentrated. Residual 1,4-dioxane was removed azeotropically using toluene (3×10 mL). The black mixture was then suspended in hexane (50 mL), vigorously stirred (1000 rpm) for 20 minutes, suction filtered onto celite, rinsed with hexane (4×20 mL), and the resulting light reddish-orange filtrate was concentrated, diluted with CHCl (10 mL), suction filtered onto silica gel, washed with CHCl (4×20 mL), and concentrated to afford the boron pinacol ester thiophene (8.303 g, 20.745 mmol, 66%, NMR purity 71%) as a reddish-orange amorphous oil. NMR indicated the product with residual BPin2 and the original debromination byproduct.

[0222] 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.71 (d, J = 3.2 Hz, 1H), 6.55 (d, J = 3.2 Hz, 1H), 5.17 (s, 2H), 3.74 (q, J = 7.1 Hz, 3H), 1.30 (s, 12H), 1.21 (t, J = 7.1 Hz, 3H). 13 CNMR (126 MHz, chloroform-d) δ 159.17, 135.96, 102.29, 94.95, 83.34, 64.16, 24.77, 15.14.

[0223] Example 20: Synthesis of the Precursor of Ligand 4

[0224]

[0225] A mixture of thiophene (4.000 g, 9.431 mmol, 3.00 equiv, 67% purity), K3PO4 (6.006 g, 28.296 mmol, 9.00 equiv), Pd(AmPhos)Cl2 (0.445 g, 0.6288 mmol, 0.20 equiv), and bisphenyliodonium (1.553 g, 3.144 mmol, 1.00 equiv) was prepared. The mixture was evacuated and then backfilled with nitrogen three more times, followed by the addition of deoxygenated 1,4-dioxane (50.0 mL) and deoxygenated water (5.0 mL) in sequence via syringe. The mixture was then placed in a hood heated to 50°C. After stirring (1000 rpm) for 36 hours, the black mixture was removed from the hood, gradually cooled to 23 ° C, filtered with suction on a silica gel pad, washed with CH2Cl2 (4×20 mL), and the transparent black filtrate was concentrated. Residual 1,4-dioxane was removed by rotary evaporation with toluene (2×10 mL). The black mixture was then suspended in CH2Cl2 (20 mL), filtered with suction on a silica gel pad, rinsed with CH2Cl2 (4×20 mL), and the black filtrate was concentrated onto celite and purified by silica gel chromatography using an ISCO chromatography purification system; 25%-100% CH2Cl2 in hexane to give bithiophene (1.376 g, 2.481 mmol, 79%) as a dark purple-black viscous oil. NMR indicated the product with trace impurities.

[0226] 1 H NMR (500MHz, chloroform-d) δ7.42 (dd, J=7.5, 1.8Hz, 2H), 7.27–7.25 (m, 4H), 6.98 (td, J=7.5, 1.1Hz, 2H), 6.90 (dd, J=8.3, 1.1Hz, 2 H), 6.66 (d, J = 3.5Hz, 2H), 5.11 (s, 4H), 3.96–3.91 (m, 4H), 3.67 (q, J = 7.1Hz, 4H), 1.82–1.77 (m, 4H), 1.20 (t, J = 7.1Hz, 6H). 13 CNMR (126 MHz, chloroform-d) δ 156.34, 153.36, 131.07, 129.85, 128.54, 123.97, 123.12, 120.29, 112.42, 100.80, 94.89, 68.02, 64.11, 26.01, 15.10.

[0227] Example 21: Synthesis of the Precursor of Ligand 4

[0228]

[0229] Before use, dithiophene was azeotropically dried using PhMe (4×10 mL). A clear, light purple solution of thiophene (1.376 g, 2.481 mmol, 1.00 equiv) in deoxygenated anhydrous THF (50 mL) in a nitrogen-filled glove box was placed in a refrigerator cooled to -35°C for 20 hours, and then a pre-cooled n-BuLi solution (2.5 mL, 6.203 mmol, 2.50 equiv, titrated to 2.50 M / hexane) was added dropwise via a syringe. The now golden-purple-brown solution was allowed to stand in the refrigerator for 3 hours, after which it was removed and solid 1,2-dibromotetrachloroethane (2.424 g, 7.443 mmol, 3.00 equiv) was added dropwise while stirring (500 rpm). After stirring at 23° C. for 2.5 hours, the now clear golden solution was removed from the glove box, neutralized with brine (50 mL), diluted with CH2Cl2 (20 mL) and water (20 mL), poured into a separatory funnel, separated, and the residual organics were extracted from the aqueous layer using CH2Cl2 (2×20 mL), combined, dried over solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography; hexane to 80% CH2Cl2 in hexane to give dibromothiophene (1.688 g, 2.369 mmol, 95%) as a golden amorphous oil. NMR indicated the product with trace impurities.

[0230] 1 H NMR (500 MHz, CHLOROFORM-d) δ 7.37 (dd, J = 7.5, 1.7 Hz, 2H), 7.28 (ddd, J = 8.3, 7.4, 1.8 Hz, 2H), 7.22 (s, 2H), 6.97 (td, J = 7.5, 1.1 Hz, 2H), 6.90 (dd, J = 8.3, 1.1 Hz, 2H), 4.82 (s, 4H), 3.97–3.93 (m, 4H), 3.48 (q, J = 7.1 Hz, 4H), 1.84–1.80 (m, 4H), 1.00 (t, J = 7.1 Hz, 6H). 13 C NMR (126 MHz, chloroform- d ) δ 156.31, 151.30, 132.47, 130.83, 129.15, 123.67, 122.86, 120.45, 112.30, 98.73, 97.05, 67.98, 65.09, 25.84, 14.81.

[0231] Example 22: Synthesis of Ligand 4

[0232]

[0233] Prior to use, the dibromide was azeotropically dried with toluene (4 x 10 mL). A solid mixture of the dibromide (0.697 g, 0.7826 mmol, 1.00 equiv), carbazole (0.654 g, 3.913 mmol, 5.00 equiv), Cu2O (0.560 g, 3.913 mmol, 5.00 equiv), and K2CO3 (2.163 g, 15.652 mmol, 20.0 equiv) in an oven-dried vial equipped with a stir bar was evacuated and then backfilled with nitrogen. This process was repeated four more times before adding deoxygenated anhydrous xylene (10.0 mL) followed by neat N,N'-dimethylethylenediamine (0.84 mL, 7.826 mmol, 10.00 equiv) via syringe. The vial was sealed with a PTFE cap under a nitrogen purge stream and placed in a hood heated to 140°C. After vigorous stirring (1000 rpm) for 72 hours, the deep red mixture was removed from the hood, gradually cooled to 23 ° C, diluted with CHCl (20 mL), and filtered with suction on silica gel using CHCl as eluent. The golden orange filtrate was concentrated onto celite and purified by silica gel chromatography; 25%-100% CHCl in hexane, and then purified twice more using 25%-65% CHCl in hexane to give biscarbazolyl-thiophene (0.155 g, 0.2153 mmol, 28%) as an off-white solid. NMR indicated the product containing trace impurities. The product was used in subsequent reactions without further purification.

[0234] To a solution of protected hydroxythiophene (0.148 g, 0.1672 mmol, 1.00 equiv) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL) at 23°C under nitrogen. After vigorous stirring (1000 rpm) for 20 hours, the light golden brown solution was diluted with aqueous HCl (20 mL, 1 N) and CHCl (20 mL), poured into a separatory funnel, and separated. The organics were washed with aqueous HCl (2 x 20 mL). The remaining organics were extracted from the aqueous layer with CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography; 25%-75% CHCl in hexanes to afford hydroxythiophene (88.1 mg, 0.1146 mmol, 69%, 14% over two steps) as a white solid. NMR indicated pure product.

[0235] 1H NMR(500MHz, chloroform-d)δ8.10(dt,J=7.6,1.0Hz,4H),7.53(dd,J=7.6,1.7Hz,2H),7.37–7.30(m,10H),7.28–7.22(m,4H),7.20( s,2H),7.15(td,J=7.5,1.1Hz,2H),6.89(dd,J=8.2,1.0Hz,2H),6.78(s,2H),4.01(d,J=4.8Hz,4H),1.88(p,J=2.5Hz,4H). 13 CNMR (126 MHz, chloroform-d) δ 154.19, 148.02, 141.96, 131.33, 130.74, 129.59, 125.98, 124.39, 123.56, 122.78, 120.30, 120.22, 119.54, 114.97, 113.55, 110.29, 69.41, 25.92.

[0236] Characterization of the protected coupling products:

[0237] 1 H NMR(500MHz, chloroform-d)δ8.11(dd,J=7.7,2.6Hz,4H),7.61–7.26(m,18H),7.10–6.98(m,4H),4.49(d ,J=3.3Hz,4H),4.14(s,4H),2.85–2.74(m,4H),2.17–2.04(m,4H),0.52(td,J=7.1,3.1Hz,6H). 13 C NMR (126 MHz, chloroform- d ) δ 156.56, 149.17, 141.91, 132.25, 131.00, 129.19, 126.20, 124.19, 123.52, 121.71, 120.60, 120.56, 120.51, 120.13, 112.21, 110.67, 96.67, 68.07, 64.40, 26.25, 14.15.

[0238] Example 23: Synthesis of Primary Catalyst 9

[0239]

[0240] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous deoxygenated C6D6 (1.26 mL) white suspension of thiophene (5.3 mg, 0.00689 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (3.1 mg, 0.00689 mmol, 1.00 equivalent) C6D6 (0.12 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. NMR indicated the product. The same procedure can be used to prepare a primary catalyst solution directly used in polymerization experiments after filtration using toluene.

[0241] 1 H NMR (500MHz, benzene-d6) δ8.11–8.03(m,2H),7.82(dt,J=7.8,1.0Hz,2H),7.63–7.57(m,2H),7.33–7.30(m,4H) ,7.30–7.23(m,6H),7.10–7.06(m,4H),7.04(ddd,J=7.9,5.2,2.8Hz,2H),6.91–6.87(m,4H),6.76–6.66(m ,6H),6.61(s,2H),6.02–5.96(m,4H),5.05(dd,J=8.2,1.3Hz,2H),4.04–3.95(m,2H),3.29(dd,J=12.2,4. 5Hz, 2H), 0.97 (d, J = 12.0Hz, 2H), 0.74 (dd, J = 17.9, 8.8Hz, 2H), 0.65–0.56 (m, 2H), 0.51 (d, J = 12.1Hz, 2H). 13 CNMR (126 MHz, benzene-d6) δ 155.56, 152.34, 146.27, 141.69, 141.30, 133.02, 131.26, 130.55, 130.13, 128.57, 128.32, 127.12, 126.66, 125.78, 125.18, 124.83, 123.10, 122.79, 120.90, 120.71, 120.51, 120.10, 119.99, 117.18, 115.08, 112.42, 109.69, 80.40, 73.80, 25.72.

[0242] Example 24: Synthesis of Primary Catalyst 10

[0243]

[0244] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous deoxygenated C6D6 (1.16 mL) white suspension of thiophene (5.0 mg, 0.00650 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added HfBn4 (3.5 mg, 0.00650 mmol, 1.00 equivalent) C6D6 (0.14 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.005 M C6D6 solution. NMR indicated the product. The same procedure can be used to prepare a primary catalyst solution for direct polymerization experiments using toluene after filtration.

[0245] 1 H NMR(500MHz, benzene-d6)δ8.13–8.07(m,2H),7.83(dt,J=7.6,1.0Hz,2H),7.61–7.54(m,2H),7.34–7.28(m,2H), 7.28–7.21(m,4H),7.10–7.05(m,4H),7.05–7.02(m,2H),6.98–6.93(m,2H),6.93–6.88(m,2H),6.77–6.66( m,6H),6.60(s,2H),6.07–6.04(m,4H),5.01(dd,J=8.2,1.3Hz,2H),4.00(dd,J=11.9,9.9Hz,2H),3.32(dd ,J=12.2,4.6Hz,2H),0.90(d,J=13.3Hz,3H),0.73–0.64(m,2H),0.53–0.46(m,2H),0.24(d,J=11.5Hz,4H). 13 CNMR (126 MHz, benzene-d6) δ 155.37, 152.31, 147.39, 141.57, 141.23, 138.51, 132.65, 131.30, 130.20, 128.67, 126.07, 125.09, 124.90, 124.33, 123.56, 122.69, 120.80, 120.75, 120.45, 120.11, 119.91, 117.01, 115.58, 112.53, 109.69, 83.00, 81.57, 25.95.

[0246] Example 25: Synthesis of Main Catalyst 11

[0247]

[0248] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous deoxygenated C6D6 (1.10 mL) white suspension of thiophene (4.7 mg, 0.00611 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn2Cl2(OEt2) (2.6 mg, 0.00822 mmol, 1.00 equivalent) C6D6 (0.11 mL) solution. After stirring (500 rpm) for 1 hour, the golden yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. NMR indicates the product containing Et2O (1.00 equivalent). The same procedure can be used to prepare the primary catalyst solution directly used in polymerization experiments after filtration using toluene.

[0249] 1 H NMR(500MHz, benzene-d6)δ8.15–8.08(m,2H),8.00(ddd,J=7.6,1.3,0.7Hz,2H),7.49–7.43(m, 2H),7.28(dt,J=8.2,1.0Hz,2H),7.23–7.20(m,4H),7.20–7.17(m,2H),7.14(dd,J=7.6,1 .1Hz,2H),6.95–6.91(m,2H),6.69–6.60(m,4H),6.58(s,2H),5.34(dd,J=7.9,1.6Hz,2H ), 4.26 (q, J = 11.5, 11.0 Hz, 2H), 3.28–3.24 (m, 2H), 0.78–0.69 (m, 2H), 0.63–0.55 (m, 2H). 13 C NMR (126 MHz, benzene-d6) δ 156.58, 151.50, 141.52, 141.42, 132.52, 130.50, 130.19, 126.64, 125.04, 124.92, 123.97, 122.48, 121.04, 120.34, 120.33, 119.55, 117.21, 116.18, 112.36, 109.58, 83.54, 26.76.

[0250] Example 26: Synthesis of Main Catalyst 12

[0251]

[0252] Before use, thiophene ligand L-4 was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C., HfBn2Cl2(OEt2) (3.4 mg, 0.00676 mmol, 1.00 equivalent) was added dropwise to a white suspension of C6D6 (1.23 mL) of thiophene (5.2 mg, 0.00676 mmol, 1.00 equivalent) in a nitrogen-filled glove box. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.005 M C6D6 solution. NMR indicated the product containing Et2O (1.00 equivalent). The same procedure can be used to prepare a primary catalyst solution for direct polymerization experiments using toluene after filtration.

[0253] 1 H NMR(400MHz, benzene-d6)δ8.13–8.05(m,2H),7.98(ddd,J=7.4,1.5,0.7Hz,2H),7.46–7 .41(m,2H),7.26(dt,J=8.3,0.9Hz,2H),7.23–7.17(m,4H),7.17–7.11(m,4H),6. 93–6.89(m,2H),6.67–6.59(m,4H),6.58(s,2H),5.36–5.30(m,2H),4.36(t,J=10 .9Hz, 2H), 3.30 (d, J = 12.7Hz, 2H), 0.72 (t, J = 9.7Hz, 2H), 0.52 (d, J = 12.2Hz, 2H). 13 C NMR (101 MHz, benzene-d6) δ 156.46, 151.77, 142.29, 141.54, 141.46, 132.30, 130.50, 130.09, 126.68, 126.00, 124.99, 124.88, 124.07, 122.45, 120.98, 120.35, 120.31, 120.27, 120.24, 119.51, 117.14, 116.57, 112.41, 110.46, 109.56, 84.24, 26.86.

[0254] Example 27: Synthesis of the precursor of ligand 5

[0255]

[0256] A clear, colorless solution of t-BuLi (6.60 mL, 11.143 mmol, 3.00 equiv., 1.70 M / pentane not titrated) in anhydrous pentane (30 mL) in a nitrogen-filled glove box was placed in a refrigerator (-35° C.) for 14 hours before solid 3,5-di-tert-butylphenyl bromide (1.000 g, 3.714 mmol, 1.00 equiv.) was added, followed by dropwise addition of pre-cooled, anhydrous, deoxygenated Et2O (5 mL). The now clear, light yellow, heterogeneous mixture was allowed to stand in the refrigerator for 3 hours before being removed from the refrigerator and neat i-PrOBPin (1.50 mL, 7.428 mmol, 2.00 equiv.) was added via syringe in a rapid, dropwise manner. The light yellow mixture was stirred (500 rpm) at 23° C. for 2 h, removed from the glove box, neutralized with aqueous phosphate buffer (50 mL, pH=8, 0.05 M), and the white heterogeneous mixture was suction filtered on a celite pad and rinsed with CH 2 Cl 2 (4×20 mL). The light yellow biphasic mixture was poured into a separatory funnel and separated. The organic matter was washed with aqueous phosphate buffer (2×25 mL, pH=8, 0.05) and washed with CH 2 Cl 2 (2×25 The remaining organic matter was extracted from the aqueous layer with 1% paraformaldehyde (5% paraformaldehyde, 0.1 ...

[0257] 1 H NMR (500 MHz, CHLOROFORM-d) δ 7.71 (d, J = 2.0 Hz, 2H), 7.58 (t, J = 2.0 Hz, 1H), 1.38 (s, 18H), 1.38 (s, 12H). 13 C NMR (126 MHz, chloroform-d) δ 149.81, 128.79, 125.55, 83.53, 34.82, 31.53, 24.89.

[0258] Example 28: Synthesis of Ligand 5

[0259]

[0260] To a vial equipped with a stir bar was added the dibromide (0.200 g, 0.2807 mmol, 1.00 equiv), K 3 PO 4 (0.715 g, 3.369 mmol, 12.0 equiv), Pd(AmPhos)Cl 2 (40.0 mg, 0.0561 mmol, 0.20 equiv), and 3,5-di-tert-butylphenylpinacol boron (0.355 g, 1.123 mmol, 4.00 equiv). The mixture was evacuated and then backfilled with nitrogen three more times before deoxygenated 1,4-dioxane (6.0 mL) and water (0.6 mL) were added sequentially via syringe. The vial was sealed with a PTFE cap under a nitrogen purge and placed in a hood heated to 50°C. After stirring (1000 rpm) for 36 hours, the purple-black mixture was removed from the hood, gradually cooled to 23° C., filtered with suction onto a silica gel pad, washed with CH 2 Cl 2 (4×20 mL), and the clear purple filtrate was concentrated onto celite and purified by silica gel chromatography using an ISCO chromatography purification system; 25%-100% CH 2 Cl 2 in hexanes to give the doubly protected coupled 3,5-di-tert-butylphenylthiophene (0.223 g, 0.2394 mmol, 85%) as a white foam. NMR indicated pure product.

[0261] To a solution of the protected bithiophene in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL). The dark golden brown solution was stirred vigorously (1000 rpm) at 23°C under nitrogen for 24 hours, then diluted with aqueous HCl (25 mL, 1 N) and CHCl (20 mL). The biphasic mixture was poured into a separatory funnel and partitioned. The organics were washed with aqueous HCl (2 x 20 mL, 1 N). The remaining organics were extracted from the aqueous layer with CHCl (2 x 10 mL). The combined organics were dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatography purification system; 25% to 100% CHCl in hexane to afford the bishydroxythiophene ligand (98.5 mg, 0.1208 mmol, 51%, 43% over two steps) as a white amorphous foam. NMR indicated pure product.

[0262] 1H NMR (500 MHz, CHLOROFORM-d) δ 7.68 (d, J = 1.7 Hz, 4H), 7.43 (dd, J = 7.6, 1.7 Hz, 2H), 7.34 (t, J = 1.8 Hz, 2H), 7.28 (ddd, J = 8.2, 7.4, 1.7 Hz, 2H), 7.10–7.06 (m, 2H), 7.06 (s, 2H), 6.96 (s, 2H), 6.89 (dd, J = 8.3, 1.2 Hz, 2H), 4.07–4.03 (m, 4H), 1.93–1.87 (m, 4H), 1.37 (s, 36H). 13 C NMR (126 MHz, chloroform- d ) δ 154.10, 150.76, 147.57, 132.94, 132.75, 131.67, 129.30, 125.03, 122.75, 121.50, 120.75, 120.66, 119.41, 114.00, 69.64, 34.92, 31.48, 25.75.

[0263] Characterization of protected ligands:

[0264] 1 H NMR (500MHz, chloroform-d) δ7.61 (d, J=1.8Hz, 4H), 7.53 (dd, J=7.5, 1.8Hz, 2H), 7.3 8(t,J=1.8Hz,2H),7.30–7.24(m,2H),7.22(s,2H),7.01(td,J=7.4,1.1Hz, 2H),6.94(dd,J=8.3,1.1Hz,2H),4.66(s,4H),4.05(d,J=5.2Hz,4H),3.16( q, J=7.0Hz, 4H), 1.99 (q, J=2.9Hz, 4H), 1.39 (s, 36H), 0.72 (t, J=7.1Hz, 6H). 13 C NMR (126 MHz, chloroform-d) δ 156.47, 150.82, 148.54, 133.49, 132.53, 131.07, 128.90, 128.73, 124.67, 122.47, 121.15, 120.86, 120.46, 112.51, 109.65, 97.06, 67.90, 64.69, 34.93, 31.50, 25.88, 14.55.

[0265] Example 29: Synthesis of Main Catalyst 13

[0266]

[0267] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.28 mL) solution of thiophene (5.8 mg, 0.00711 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.14 mL) solution of ZrBn4 (3.3 mg, 0.00711 mmol, 1.00 equivalent). After stirring (500 rpm) for 45 minutes, the golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. The same procedure can be used to prepare a primary catalyst solution directly used in polymerization experiments after filtration using toluene.

[0268] 1 H NMR(500MHz, benzene-d6)δ7.78(d,J=1.8Hz,4H),7.56(t,J=1.8Hz,2H),7.20–7.17(m,2H),7.1 2–7.11(m,2H),6.99–6.95(m,2H),6.90–6.82(m,4H),6.76(tt,J=7.4,1.2Hz,2H),6.69(s ,2H),6.63–6.58(m,4H),5.92–5.87(m,2H),4.17(dd,J=11.9,10.1Hz,2H),3.51(dd,J=11 .8, 4.8Hz, 2H), 1.33 (s, 36H), 1.32 (s, 4H), 0.77 (t, J = 9.4Hz, 2H), 0.46 (d, J = 12.1Hz, 2H). 13 C NMR (126 MHz, benzene-d6) δ 155.93, 153.46, 151.24, 147.65, 134.39, 133.79, 131.53, 130.07, 128.15, 126.24, 123.51, 123.41, 121.75, 121.03, 120.83, 119.16, 80.99, 76.61, 34.72, 31.31, 26.86.

[0269] Example 30: Synthesis of Main Catalyst 14

[0270]

[0271] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C., a solution of anhydrous C6D6 (1.48 mL) of thiophene (6.7 mg, 0.00822 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.18 mL) solution of HfBn4 (4.5 mg, 0.00822 mmol, 1.00 equivalent). After stirring (500 rpm) for 45 minutes, the golden yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.005 M C6D6 solution. The same procedure can be used to prepare a primary catalyst solution that is directly used in polymerization experiments after filtration using toluene.

[0272] 1 H NMR (500MHz, benzene-d6) δ7.75(d,J=1.9Hz,4H),7.56(t,J=1.8Hz,2H),7.20–7.15(m,2H),7.12(td,J =1.7,1.3,0.7Hz,4H),6.92–6.83(m,4H),6.74(tt,J=7.3,1.3Hz,2H),6.69(s,2H),6.62–6.57(m ,4H),5.92(dd,J=8.0,1.4Hz,2H),4.30–4.23(m,2H),3.58(dd,J=12.5,4.9Hz,2H),2.42(d,J=1 2.7Hz, 2H), 1.45 (d, J = 12.8Hz, 2H), 1.33 (s, 36H), 0.78 (t, J = 9.6Hz, 2H), 0.41 (d, J = 11.4Hz, 2H). 13 C NMR (126 MHz, benzene-d6) δ 155.90, 153.51, 151.23, 147.91, 134.12, 133.72, 131.54, 130.05, 128.91, 126.83, 126.35, 123.60, 123.55, 121.72, 121.25, 121.21, 119.10, 81.77, 80.32, 34.71, 31.32, 27.04.

[0273] Example 31: Synthesis of Ligand 6

[0274]

[0275] A mixture of the dibromide (200.0 mg, 0.2807 mmol, 1.00 equiv), Pd(AmPhos)Cl2 (40.0 mg, 0.0564 mmol, 0.20 equiv), K3PO4 (536.0 mg, 2.526 mmol, 9.00 equiv) and boropinacol (351.0 mg, 0.8421 mmol, 3.00 equiv) was evacuated and backfilled with nitrogen four more times before the addition of freshly bubbled deoxygenated 1,4-dioxane (3.0 mL) and H2O (0.3 mL) in that order. The canary yellow mixture was then placed in a mantle heated to 50° C. and stirred vigorously (1000 rpm) for 24 hours. The dark gray mixture was removed from the mantle, allowed to cool to ambient temperature, diluted with CHCl (20 mL), suction filtered over a pad of silica gel, rinsed with CHCl (4×20 mL), and the resulting filtrate concentrated onto celite and purified by silica gel chromatography; 10% CHCl to 50% CHCl in hexanes, and then purified again by silica gel chromatography; 35% CHCl in hexanes to give the protected coupled product (101.0 mg, 0.0893 mmol, 32%) as an off-white foam. NMR indicated pure product.

[0276] To a solution of protected coupled bithiophene (101.0 mg, 0.0893 mmol, 1.00 equiv) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (3 mL, 37% aqueous solution) via syringe under nitrogen. The golden solution was stirred (500 rpm) for 16 hours, diluted with aqueous HCl (10 mL, 1 N) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics washed with aqueous HCl (1 x 10 mL, 1 N). The remaining organics were extracted from the aqueous solution with CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography; 10%-35% CHCl in hexane to afford bis-hydroxythiophene (90.4 mg, 0.0890 mmol, 99%, 32% over two steps) as a white foam. NMR indicated pure product.

[0277] 1H NMR (500 MHz, chloroform-d) δ 8.45 (s, 2H), 7.98 (d, J = 8.9 Hz, 2H), 7.95–7.90 (m, 4H), 7.90–7.87 (m, 2H), 7.65–7.53 (m, 4H), 7.49 (ddd, J = 9.2, 7.1, 2.0 Hz, 2H), 7.44 (d, J = 3.6 Hz, 2H ),7.30–7.23(m,2H),7.12(t,J=7.5Hz,2H),6.76(d,J=8.2Hz,2H),6.47(d,J=6.4Hz ,2H),3.97–3.86(m,4H),1.90–1.80(m,4H),1.42(s,9H),1.41(s,9H),1.33(s,18H). 13 C NMR (126 MHz, chloroform-d) δ 154.35, 149.39, 147.73, 147.04, 131.88, 131.50, 131.35, 130.92, 130.67, 130.33, 129.08, 128.05, 127.32, 126.21, 125.47, 125.2 9,124.90,124.56,122.81,122.42,122.41,122.39,120.76,114.67,114.65,113.57,113.53,69.12,69.08,35.06,30.97,30.95,30.91,25.87,25.83.

[0278] Characterization of the protected coupling products:

[0279] 1 H NMR (500 MHz, chloroform-d) δ8.44 (s, 2H), 8.04–7.96 (m, 4H), 7.97–7.88 (m, 4H), 7.64 (dd, J = 7.6, 1.8 Hz, 2H), 7.59 (s, 2H), 7.57 (ddd, J = 8.9, 6.4, 2.1 Hz, 4H), 7.30 (td, J = 7.8, 1.8 Hz, 2H), 7.04 ( td,J=7.4,1.0Hz,2H),7.01(d,J=8.3Hz,2H),4.42(q,J=5.9Hz,4H),4.14(d,J=5.1Hz,4H),2 .64(q,J=7.1Hz,4H),2.13–2.05(m,4H),1.44(s,18H),1.39(s,18H),0.42(t,J=7.0Hz,6H). 13C NMR (126 MHz, chloroform-d) δ 156.55, 151.02, 147.67, 147.12, 132.01, 132.00, 131.66, 131.28, 131.17, 130.66, 130.09, 128.68, 127.83, 127.19, 126.45, 125.91, 125.48,124.74,124.74,124.55,123.58,122.52,121.78,121.21,120.49,112.51,96.57,68.04,64.08,35.10,34.81,30.97,30.93,29.72,26.18,14.17.

[0280] Example 32: Synthesis of Ligand 7

[0281]

[0282] Before use, the dibromide was azeotropically dried with toluene (4 x 10 mL). A solid mixture of the dibromide (0.850 g, 1.193 mmol, 1.00 equiv), carbazole (1.667 g, 5.965 mmol, 5.00 equiv), Cu2O (0.854 g, 5.965 mmol, 5.00 equiv), and K2CO3 (3.300 g, 23.860 mmol, 20.0 equiv) in an oven-dried flask equipped with a stir bar and reflux condenser was evacuated and then backfilled with nitrogen four more times before adding deoxygenated anhydrous xylene (20.0 mL) followed by neat N,N'-dimethylethylenediamine (1.30 mL, 11.930 mmol, 10.00 equiv) via syringe. After vigorous stirring (1000 rpm) for 72 hours, the dark red heterogeneous mixture was removed from the hood, allowed to gradually cool to 23° C., diluted with CHCl (30 mL), vigorously stirred (1000 rpm) for 2 minutes, and suction filtered over silica gel using CHCl as the eluent, rinsing with CHCl (4×25 mL). The golden orange filtrate was concentrated onto celite and purified by silica gel chromatography; 45% CHCl in hexanes to give biscarbazolyl-thiophene (0.317 g, 0.2857 mmol, 24%) as a golden foam. NMR indicated the product contained trace impurities. The product was used in subsequent reactions without further purification.

[0283] To a solution of protected hydroxythiophene (0.317 g, 0.2857 mmol, 1.00 equiv) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL) at 23°C under nitrogen. After vigorous stirring (1000 rpm) for 16 hours, the light golden brown solution was diluted with aqueous HCl (20 mL, 1 N) and CHCl (20 mL), poured into a separatory funnel, and separated. The organics were washed with aqueous HCl (2 x 20 mL). The remaining organics were extracted from the aqueous layer with CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography; 10%-30% CHCl in hexanes to afford hydroxythiophene (0.252 g, 0.2537 mmol, 89%, 21% over two steps) as a golden foam. NMR indicated pure product.

[0284] 1 H NMR (500MHz, chloroform-d) δ8.10(d,J=1.8Hz,4H),7.53(dd,J=7.6,1.7Hz,2H),7.39(dd,J=8.6,1.9Hz,4H),7.32(td,J=7.8,1.7Hz,2H),7.23(d,J=8.5 Hz,4H),7.18(s,2H),7.12(td,J=7.5,1.1Hz,2H),6.91(dd,J=8.3,1.1H z,2H),6.66(s,2H),4.07–4.03(m,4H),1.91–1.87(m,4H),1.43(s,36H). 13 C NMR (126 MHz, chloroform-d) δ 154.34, 147.72, 143.16, 140.41, 131.33, 130.56, 129.51, 124.52, 123.60, 123.51, 122.66, 119.31, 116.25, 115.50, 113.48, 109.66, 69.47, 34.70, 32.01, 26.03.

[0285] Characterization of protected ligands:

[0286] 1H NMR (500MHz, chloroform-d) δ8.10(d,J=2.0Hz,4H),7.55(dd,J=7.5,1.8Hz,2H),7.45(dd,J=8.6,1.9Hz,4H),7.36(d,J=8.6Hz,4H),7.34–7.30(m,2H), 7.29(s,2H),7.07–6.98(m,4H),4.50(s,4H),4.18–4.11(m,4H),2.83(q ,J=7.0Hz,4H),2.13–2.03(m,4H),1.45(s,36H),0.55(t,J=7.0Hz,6H). 13 C NMR (126 MHz, chloroform-d) δ 156.62, 148.96, 143.32, 140.40, 132.13, 131.05, 129.11, 124.38, 123.83, 123.44, 122.05, 120.51, 120.38, 116.06, 112.16, 110.00, 96.74, 68.17, 64.44, 34.73, 32.01, 26.37, 14.19.

[0287] Example 33: Synthesis of Main Catalyst 17

[0288]

[0289] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.25 mL) transparent colorless solution of thiophene (15.6 mg, 0.0157 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (7.2 mg, 0.0157 mmol, 1.00 equivalent) C6D6 (0.30 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.01 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) directly used in polymerization experiments after filtration.

[0290] 1H NMR (400MHz, benzene-d6) δ8.42(d,J=1.8Hz,2H),8.19(d,J=1.9Hz,2H),7.64(d,J=8.5Hz,2H),7.46(ddd,J=8.7,5.8,1.9 Hz,4H),7.28(d,J=8.7Hz,2H),7.10–7.00(m,2H),6.97–6.93(m,2H),6.80–6.67(m,6H),6.62(s,2H),6.35–6.29(m ,2H),6.14–6.06(m,4H),5.18(dd,J=7.9,1.4Hz,2H),4.04(t,J=10.5Hz,2H),3.35(dd,J=11.8,4.5Hz,2H),1.45(s ,18H),1.26(s,18H),0.99(d,J=12.1Hz,2H),0.76(t,J=9.1Hz,2H),0.61(t,J=12.8Hz,2H),0.46(d,J=12.2Hz,2H). 13 C NMR (101 MHz, benzene-d6) δ 155.80, 151.78, 146.61, 143.34, 143.08, 139.98, 139.59, 133.04, 131.33, 130.53, 130.21, 128.88, 128.30, 126.71, 125.79, 125.26, 124.87, 123.21, 122.80, 122.74, 120.78, 116.56, 116.38, 115.83, 115.71, 112.39, 109.35, 80.63, 74.21, 34.55, 34.39, 31.94, 31.68, 25.88.

[0291] Example 34: Synthesis of Main Catalyst 18

[0292]

[0293] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C., a transparent, colorless solution of anhydrous C6D6 (1.00 mL) of thiophene (13.3 mg, 0.01339 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.31 mL) solution of HfBn4 (7.3 mg, 0.01339 mmol, 1.00 equivalent). After stirring (500 rpm) for 1 hour, the light golden yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.01 M C6D6 solution. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0294] 1 H NMR (400MHz, benzene-d6) δ8.44(d,J=1.8Hz,2H),8.19(d,J=1.8Hz,2H),7.65–7.60(m,2H),7.45(ddd,J=10.7,8.6,1.9Hz ,4H),7.19(dd,J=8.6,0.6Hz,2H),7.10–7.03(m,2H),6.95(ddq,J=7.3,1.4,0.7Hz,2H),6.78–6.73(m,4H),6.74–6 .68(m,4H),6.61(s,2H),6.16–6.10(m,4H),5.18(dd,J=8.1,1.3Hz,2H),4.07(t,J=10.8Hz,2H),3.43–3.34(m,2H) ,1.46(s,18H),1.26(s,18H),0.87(d,J=13.2Hz,2H),0.79–0.68(m,2H),0.57–0.47(m,2H),0.19(d,J=13.2Hz,2H). 13 C NMR (126 MHz, benzene-d6) δ 155.63, 151.81, 147.60, 143.41, 143.11, 139.92, 139.58, 132.72, 131.40, 130.30, 128.96, 128.15, 127.99, 127.28, 126.99, 126.91, 12 6.04,125.29,124.96,123.58,122.73,122.67,120.76,116.45,116.38,116.29,115.64,112.53,109.37,81.66,78.32,34.57,34.41,31.97,31.70,26.09.

[0295] Example 35: Synthesis of Ligand 8

[0296]

[0297] A mixture of the dibromide (361.5 mg, 0.5074 mmol, 1.00 equiv), Pd(AmPhos)Cl2 (72.0 mg, 0.1015 mmol, 0.20 equiv), K3PO4 (969.0 mg, 4.566 mmol, 9.00 equiv) and m-terphenylboropinacolate (542.0 mg, 1.522 mmol, 3.00 equiv) was evacuated and backfilled with nitrogen four more times before the addition of freshly bubbled deoxygenated 1,4-dioxane (6.0 mL) and H2O (0.8 mL) in that order. The canary yellow mixture was then placed in a mantle heated to 50° C. and stirred vigorously (1000 rpm) for 48 hours. The dark gray mixture was removed from the mantle, allowed to cool to ambient temperature, diluted with CHCl (20 mL), suction filtered over a pad of silica gel, rinsed with CHCl (4×20 mL), and the resulting filtrate concentrated onto celite and purified by silica gel chromatography; 10% CHCl to 65% CHCl in hexanes to give the protected coupled product (393.0 mg, 0.3886 mmol, 77%) as an off-white foam. NMR indicated the product with trace impurities.

[0298] To a solution of protected coupled bithiophene (393.0 mg, 0.3886 mmol, 1.00 equiv) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL, 37% aqueous solution) via syringe under nitrogen. The golden solution was stirred (500 rpm) for 20 hours, diluted with aqueous HCl (10 mL, 1 N) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics washed with aqueous HCl (1 x 10 mL, 1 N). The remaining organics were extracted from the aqueous solution with CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography; 25%-55% CHCl in hexane to afford bis-hydroxythiophene (213.0 mg, 0.2380 mmol, 61%, 47% over two steps) as a white foam. NMR indicated pure product.

[0299] 1H NMR (500MHz, chloroform-d) δ8.15(d,J=1.7Hz,4H),7.79(d,J=1.4Hz,4H),7.77(q,J=1.3Hz,6H),7.57–7.50(m,8H),7.47–7.42(m,6H), 7.31–7.25(m,2H),7.12(s,2H),7.10(td,J=7.5,1.1Hz,2H),6.88(dd,J=8.3,1.0Hz,2H),4.11–3.99(m,4H),1.98–1.88(m,4H). 13 C NMR (126 MHz, chloroform-d) δ 154.04, 148.57, 142.10, 141.35, 135.00, 133.04, 131.71, 129.55, 128.90, 127.55, 127.42, 124.75, 124.74, 124.24, 122.93, 120.27, 119.49, 114.03, 69.85, 25.93.

[0300] Characterization of protected ligands:

[0301] 1 H NMR (500MHz, chloroform-d) δ7.98(d,J=1.6Hz,4H),7.74(d,J=1.9Hz,2H),7.70(d,J=7.4Hz,8H),7.54–7.43(m,10H),7.43–7.35(m,4H),7.29–7.21(m,4H) ,6.99(t,J=7.4Hz,2H),6.87(d,J=8.2Hz,2H),4.71(s,4H),4.00(d,J=5. 3Hz, 4H), 3.19 (q, J = 7.0Hz, 4H), 2.04–1.89 (m, 4H), 0.73 (t, J = 7.0Hz, 6H). 13 C NMR (126 MHz, chloroform-d) δ 156.42, 149.33, 142.07, 140.99, 134.37, 133.67, 130.96, 128.89, 128.83, 127.54, 127.52, 127.26, 125.64, 124.80, 124.42, 121.59, 120.50, 112.52, 97.35, 68.03, 64.97, 26.05, 14.57.

[0302] Example 36: Synthesis of Main Catalyst 19

[0303]

[0304] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.05 mL) transparent colorless solution of thiophene (9.3 mg, 0.0104 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (4.7 mg, 0.0104 mmol, 1.00 equivalent) C6D6 (0.19 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.01 M C6D6 solution. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) directly used in polymerization experiments after filtration.

[0305] 1 H NMR (400MHz, benzene-d6) δ8.38(d,J=1.7Hz,4H),7.73(t,J=1.7Hz,2H),7.61–7.55(m,8H),7.17–7.12(m, 8H),7.11–6.92(m,12H),6.77(td,J=7.4,1.3Hz,2H),6.71(ddt,J=9.2,7.5,1.6Hz,4H),6.67(s,2H) ,6.35–6.30(m,4H),6.19(dd,J=8.1,1.3Hz,2H),4.14(dd,J=11.9,9.9Hz,2H),3.47(dd,J=12.0,4. 6Hz, 2H), 2.28 (d, J = 12.1Hz, 2H), 1.53 (d, J = 12.0Hz, 2H), 0.84–0.73 (m, 2H), 0.47 (d, J = 12.0Hz, 2H). 13 C NMR (101 MHz, benzene-d6) δ 155.21, 154.56, 147.21, 142.96, 141.03, 135.65, 135.24, 131.66, 130.03, 129.45, 128.73, 128.15, 126.62, 126.12, 125.38, 124.70, 123.11, 121.04, 119.70, 119.02, 80.45, 76.42, 26.58.

[0306] Example 37: Synthesis of Primary Catalyst 20

[0307]

[0308] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C., a transparent, colorless solution of anhydrous C6D6 (1.00 mL) of thiophene (10.3 mg, 0.0115 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.27 mL) solution of HfBn4 (6.3 mg, 0.0115 mmol, 1.00 equivalent). After stirring (500 rpm) for 1 hour, the light golden yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.01 M C6D6 solution. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0309] 1 H NMR(400MHz, benzene-d6)δ8.36(d,J=1.7Hz,4H),7.74(t,J=1.7Hz,2H),7.62–7.56(m,8H),7. 19–7.12(m,8H),7.12–6.93(m,10H),6.81–6.67(m,6H),6.66(s,2H),6.37–6.32(m,4H) ,6.21(dd,J=8.0,1.4Hz,2H),4.28–4.17(m,2H),3.52(dd,J=12.2,4.7Hz,2H),2.11(d, J=13.0Hz,2H),1.33(d,J=13.0Hz,2H),0.80(dd,J=14.1,6.2Hz,2H),0.47–0.35(m,2H). 13 C NMR (101 MHz, benzene-d6) δ 155.13, 154.62, 147.58, 142.94, 141.03, 137.46, 135.60, 134.98, 131.65, 130.05, 129.42, 128.73, 128.15, 127.19, 127.17, 126.28, 125.28, 124.65, 123.28, 121.18, 119.65, 119.48, 81.28, 80.66, 26.74.

[0310] Example 38: Synthesis of the Boron Pinacolate Intermediate of Ligand 8

[0311]

[0312] In a nitrogen-filled glove box, bromo-m-terphenyl (3.350 g, 10.834 mmol, 1.00 equiv), Pd(dppf)Cl2 (0.442 g, 0.5417 mmol, 0.05 equiv), B2Pin2 (4.127 g, 16.251 mmol, 1.50 equiv) and KOAc (3.190 g, 32.502 mmol, 3.00 equiv) were dissolved in anhydrous deoxygenated 1,4-dioxane (100 mL). The mixture was placed in a mantle heated to 100° C. and stirred vigorously (1000 rpm) for 24 hours. The mixture was removed from the heating mantle, allowed to gradually cool to 23° C., and filtered through a pad of silica gel with CH 2 Cl 2 (4×25 mL) and the resulting filtrate was concentrated onto celite and purified by silica gel chromatography; 10% CH 2 Cl 2 to 100% CH 2 Cl 2 in hexanes to afford the boropinacolate (3.446 g, 9.672 mmol, 89%) as a white solid. NMR indicated pure product.

[0313] 1 H NMR (500MHz, chloroform-d) δ8.08(dt,J=2.7,1.7Hz,2H),7.95(p,J=2.0Hz,1H),7.73(dq,J=7.9,1.5Hz ,4H),7.48(tt,J=8.0,1.5Hz,4H),7.39(ddt,J=8.3,6.9,1.3Hz,2H),1.42(s,6H),1.41(s,6H). 13 C NMR (126 MHz, chloroform-d) δ 141.15, 141.09, 132.49, 128.91, 128.68, 127.36, 127.31, 83.95, 24.90.

[0314] Example 39: Synthesis of Ligand 9

[0315]

[0316] A mixture of the dibromide (268.7 mg, 0.3771 mmol, 1.00 equiv), Pd(AmPhos)Cl2 (53.0 mg, 0.0754 mmol, 0.20 equiv), K3PO4 (720.0 mg, 3.394 mmol, 9.00 equiv) and m-bis(3,5-di-tert-butylphenyl)terphenylboropinacolate (689.0 mg, 1.186 mmol, 3.15 equiv) was evacuated and backfilled with nitrogen four more times before the addition of freshly bubbled deoxygenated 1,4-dioxane (7.5 mL) and H2O (1.0 mL) in that order. The canary yellow mixture was then placed in a mantle heated to 50° C. and stirred vigorously (1000 rpm) for 48 hours. The dark gray mixture was removed from the mantle, allowed to cool to ambient temperature, diluted with CHCl (20 mL), suction filtered over a pad of silica gel, rinsed with CHCl (4×20 mL), and the resulting filtrate concentrated onto celite and purified by silica gel chromatography; 10% CHCl to 50% CHCl in hexanes to give the protected coupled product (476.0 mg, 0.3260 mmol, 86%) as an off-white foam. NMR indicated pure product.

[0317] To a solution of protected coupled bithiophene (476.0 mg, 0.3260 mmol, 1.00 equiv) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL, 37% aqueous solution) via syringe under nitrogen. The golden solution was stirred (500 rpm) for 24 hours, diluted with aqueous HCl (10 mL, 1 N) and CHCl (10 mL), poured into a separatory funnel, and separated. The organics were washed with aqueous HCl (1 x 10 mL, 1 N). The residual organics were extracted from the aqueous layer with CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography; 10%-25% CHCl in hexane to afford bis-hydroxythiophene (251.0 mg, 0.1868 mmol, 57%) as a white foam. NMR indicated pure product.

[0318] 1H NMR (400MHz, chloroform-d) δ8.02(d,J=1.6Hz,4H),7.65(t,J=1.7Hz,2H),7.52(s,4 H),7.51(s,4H),7.48(t,J=1.8Hz,4H),7.41(dd,J=7.6,1.7Hz,2H),7.24(td ,J=7.7,1.7Hz,2H),7.08(d,J=4.9Hz,4H),7.05(td,J=7.5,1.0Hz,2H),6.85 (dd,J=8.3,1.1Hz,2H),4.10–4.01(m,4H),1.95–1.85(m,4H),1.39(s,72H). 13 C NMR (101 MHz, chloroform-d) δ 153.95, 151.14, 148.35, 143.27, 141.04, 134.49, 132.94, 131.67, 129.45, 125.13, 124.87, 124.72, 122.79, 122.01, 121.52, 120.04, 119.60, 113.86, 69.68, 35.01, 31.55, 25.79.

[0319] Characterization of the protected coupling products:

[0320] 1 H NMR (400MHz, chloroform-d) δ7.94(d,J=1.6Hz,4H),7.70(d,J=1.8Hz,2H),7.52–7.49(m,14H),7.28–7.18(m,4H),6.97(t,J=7.4Hz,2H),6.85(d, J=8.3Hz,2H),4.71(s,4H),3.99(d,J=5.4Hz,4H),3.19(q,J=7.0Hz,4H),1.96(q,J=3.4,2.9Hz,4H),1.41(s,72H),0.72(t,J=7.0Hz,6H). 13 C NMR (101 MHz, chloroform-d) δ 156.35, 151.21, 149.18, 143.32, 140.80, 133.99, 133.52, 130.97, 128.81, 127.74, 125.82, 125.79, 124.30, 121.92, 121.64, 121.53, 120.39, 112.33, 97.24, 67.89, 64.98, 35.02, 31.56, 25.99, 14.57.

[0321] Example 40: Synthesis of Main Catalyst 21

[0322]

[0323] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.00 mL) transparent colorless solution of thiophene (17.5 mg, 0.01302 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (5.9 mg, 0.01302 mmol, 1.00 equivalent) C6D6 (0.24 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.01 M C6D6 solution. The same procedure can be used to prepare a primary catalyst solution (0.005 M) directly used in polymerization experiments after filtration using toluene.

[0324] 1 H NMR (400MHz, benzene-d6) δ8.44(d,J=1.6Hz,4H),8.04(t,J=1.7Hz,2H),7.68(d,J=1.8Hz,8H),7.45(t,J=1.8 Hz,4H),7.12–7.00(m,2H),6.99–6.93(m,2H),6.91–6.83(m,6H),6.70–6.64(m,2H),6.61(s,2H),6.21 (dd,J=8.3,1.1Hz,2H),6.15–6.10(m,4H),4.15(t,J=10.7Hz,2H),3.50(dd,J=12.0,3.5Hz,2H),2.15( d,J=12.3Hz,2H),1.55(d,J=12.3Hz,2H),1.23(s,72H),0.75–0.65(t,J=9.3Hz,2H),0.43–0.30(m,2H). 13 C NMR (101 MHz, benzene-d6) δ 155.73, 154.60, 151.09, 147.57, 144.73, 141.38, 135.46, 134.94, 131.48, 130.10, 129.57, 128.15, 127.17, 126.18, 126.02, 125.88, 125.55, 123.19, 122.10, 121.60, 120.67, 119.56, 119.22, 80.64, 77.44, 34.62, 31.24, 26.57.

[0325] Example 41: Synthesis of Primary Catalyst 22

[0326]

[0327] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C., a transparent, colorless solution of anhydrous C6D6 (1.05 mL) of thiophene (18.2 mg, 0.01354 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.30 mL) solution of HfBn4 (7.4 mg, 0.01354 mmol, 1.00 equivalent). After stirring (500 rpm) for 1 hour, the light golden yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.01 M C6D6 solution. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0328] 1 H NMR (400MHz, benzene-d6) δ8.42(d,J=1.6Hz,4H),8.05(t,J=1.7Hz,2H),7.70(d,J=1.8Hz,8H),7.45( t,J=1.8Hz,4H),7.12–7.05(m,4H),7.01–6.83(m,6H),6.69–6.63(m,2H),6.60(s,2H),6.25(dd ,J=8.7,1.1Hz,2H),6.17–6.11(m,4H),4.24(t,J=10.9Hz,2H),3.56(d,J=11.9Hz,2H),1.97(d, J=13.2Hz,2H),1.33(d,J=13.3Hz,2H),1.24(s,72H),0.69(t,J=9.7Hz,2H),0.34–0.24(m,2H). 13 C NMR (126 MHz, benzene-d6) δ 155.67, 154.67, 151.12, 147.89, 144.71, 141.38, 135.43, 134.72, 131.49, 130.16, 129.55, 128.17, 128.13, 127.99, 127.29, 126.94, 126.86, 126.03, 125.92, 125.49, 123.40, 122.11, 121.64, 120.88, 119.67, 119.53, 81.49, 81.31, 34.65, 31.26, 26.78.

[0329] Example 42: Synthesis of Ligand 9 Boron Pinacolate

[0330]

[0331] To a pre-cooled solution of t-BuLi (3.6 mL, 6.122 mmol, 3.30 equiv, 1.7 M / pentane) in anhydrous deoxygenated pentane (20 mL) in a nitrogen-filled glove box was added dropwise a pre-cooled solution of 3,5-bis-(3,5-di-tert-butylphenyl)-m-terphenyl bromide (0.990 g, 1.855 mmol, 1.00 equiv) in pentane / EtO (20 mL, 1:1) at -35°C (pre-cooled for 16 hours) over 10 minutes. The now golden mixture was placed in the refrigerator (-35°C) for 4 hours before neat i-PrOBPin (1.25 mL, 6.122 mmol, 3.30 equiv) was added via syringe. The now light yellow heterogeneous mixture was stirred at 23° C. for 3 hours. i-PrOH (3 mL) was added to neutralize any residual t-BuLi. The mixture was removed from the glove box, water (20 mL) and Et2O (30 mL) were added, the biphasic mixture was stirred for 2 minutes, poured into a separatory funnel, separated, and the organics were washed with water (2×25 mL). The residual organics were extracted with Et2O (2×25 mL), combined, dried over solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography on an ISCO; hexanes to 50% CHCl in hexanes to give mesitylene-m-terphenylboropinacolate (0.689 g, 1.187 mmol, 64%) as a white foam. NMR indicated pure product.

[0332] 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.07 (s, 2H), 7.95 (s, 1H), 7.60–7.50 (m, 6H), 1.48 (s, 36H), 1.46 (s, 12H). 13 C NMR (101 MHz, chloroform-d) δ 151.11, 142.63, 141.07, 132.62, 130.23, 122.12, 121.46, 83.93, 35.08, 31.67, 24.95.

[0333] Example 43: Synthesis of the bromide intermediate of ligand 9

[0334]

[0335] A mixture of tribromobenzene (2.299 g, 7.303 mmol, 1.00 equiv), 3,5-di-tert-butylphenylboropinacol (6.237 g, 19.719 mmol, 2.70 equiv), Pd(PPh3)4 (0.844 g, 0.7303 mmol, 0.10 equiv) and K2CO3 (8.176 g, 59.154 mmol, 8.10 equiv) equipped with a reflux condenser was evacuated and then backfilled with nitrogen. This evacuation / refilling process was repeated three more times. Fresh deoxygenated ether was added simultaneously via syringe. The mixture was stirred for 24 hours in a hood heated to 70°C and stirred vigorously (1000 rpm). The mixture was removed from the hood and allowed to gradually cool to 23°C. The golden suspension was filtered through silica gel with suction, rinsed with CH2Cl2 (4×20 mL), and the yellow filtrate was concentrated onto celite and purified by silica gel chromatography; hexane to give 3,5-bis-(3,5-di-tert-butylphenyl)phenyl bromide (0.990 g, 1.855 mmol, 25%) as a white solid. NMR indicated pure product.

[0336] 1 H NMR (500 MHz, CHLOROFORM-d) δ 7.72–7.69 (m, 3H), 7.52 (t, J = 1.8 Hz, 2H), 7.44 (d, J = 1.8 Hz, 4H), 1.42 (s, 36H). 13 C NMR (126 MHz, chloroform-d) δ 151.45, 144.95, 139.54, 128.98, 125.69, 122.87, 122.12, 121.81, 35.05, 31.54.

[0337] Example 44: Synthesis of Ligand 10

[0338]

[0339] To a vial equipped with a stir bar was added the dibromide (0.407 g, 0.5712 mmol, 1.00 equiv), K 3 PO 4 (1.091 g, 5.141 mmol, 9.0 equiv), Pd(AmPhos)Cl 2 (81.0 mg, 0.1142 mmol, 0.20 equiv), and anthrylboropinacol (0.960 g, 1.588 mmol, 2.78 equiv). The mixture was evacuated and then backfilled with nitrogen three more times before deoxygenated 1,4-dioxane (6.0 mL) and water (0.6 mL) were added sequentially via syringe. The vial was sealed with a PTFE cap under a nitrogen purge and placed in a hood heated to 50°C. After stirring (1000 rpm) for 36 hours, the purple-black mixture was removed from the hood, gradually cooled to 23 ° C, filtered on a silica gel pad, washed with CH2Cl2 (4×20 mL), and the transparent purple filtrate was concentrated. The residual 1,4-dioxane was removed by azeotropic evaporation with toluene (3×10 mL). The resulting black mixture was suspended in CH2Cl2 (10 mL) and filtered through silica gel to remove residual insoluble impurities. It was washed with CH2Cl2 (4×20 mL). The purple filtrate was concentrated onto diatomaceous earth and purified by silica gel chromatography using an ISCO chromatography purification system; 25%-65% CH2Cl2 in hexane to obtain double-protected coupled thiophene (0.588 g, 0.3899 mmol, 68%) as a golden foam. NMR indicated pure product.

[0340] To a solution of the protected bithiophene in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL). The dark golden brown solution was vigorously stirred (1000 rpm) at 23°C under nitrogen for 24 hours, then diluted with aqueous HCl (25 mL, 1 N) and CHCl (20 mL). The biphasic mixture was poured into a separatory funnel and partitioned. The organics were washed with aqueous HCl (2 x 20 mL, 1 N). The remaining organics were extracted from the aqueous layer with CHCl (2 x 10 mL). The combined organics were dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatography purification system; 25%-80% CHCl in hexane to afford the bishydroxythiophene ligand (0.373 g, 0.2680 mmol, 69%, 47% over two steps) as a golden amorphous foam. NMR indicated pure product.

[0341] 1H NMR (500MHz, chloroform-d) δ8.02(d,J=9.2Hz,4H),7.78(d,J=2.0Hz,4H),7.65(dd,J=7.6,1.7Hz,2H ),7.60(t,J=1.9Hz,2H),7.52(dd,J=9.2,2.0Hz,4H),7.48(s,2H),7.40(dt,J=8.1,1.7Hz,4H ),7.29(td,J=7.8,1.8Hz,2H),7.15(td,J=7.5,1.1Hz,2H),6.85–6.78(m,2H),6.64(s,2H), 4.01(d,J=4.7Hz,4H),1.95(q,J=2.9,2.2Hz,4H),1.47(s,18H),1.46(s,18H),1.29(s,36H). 13 C NMR (126 MHz, chloroform-d) δ 154.37, 150.32, 150.29, 149.60, 146.76, 139.56, 137.84, 131.58, 131.22, 130.21, 129.20, 126.28, 125.97, 124.96, 124.93, 124.61, 122.54, 122.23, 121.97, 120.49, 115.31, 113.56, 69.40, 35.07, 34.92, 31.71, 31.69, 30.92, 26.06.

[0342] Characterization of protected ligands:

[0343] 1 H NMR (400MHz, chloroform-d) δ8.02(d,J=9.3Hz,4H),7.67(d,J=1.9Hz,4H),7.60(dd,J=7.5,1.8Hz,2H),7.52 (t,J=1.8Hz,2H),7.51(d,J=0.9Hz,3H),7.48(d,J=2.0Hz,2H),7.29(dt,J=11.3,1.6Hz,4H),7.26– 7.23(m,2H),7.00(td,J=7.5,1.0Hz,2H),6.97(dd,J=8.3,1.0Hz,2H),4.45(s,4H),4.14(m,4H),2. 68(q,J=7.0Hz,4H),2.10(m,4H),1.39(s,18H),1.38(s,18H),1.24(s,36H),0.44(t,J=7.0Hz,6H). 13C NMR (101 MHz, chloroform-d) δ 156.67, 151.30, 150.27, 150.18, 146.73, 139.47, 137.70, 132.60, 131.26, 130.00, 129.93, 128.73, 126.44, 125.94, 125.78, 125 .16,124.84,124.71,123.17,122.24,121.62,120.48,120.37,112.28,96.86,68.12,64.20,34.98,34.96,34.87,31.61,31.59,30.83,26.25,14.17.

[0344] Example 45: Synthesis of Primary Catalyst 23

[0345]

[0346] Prior to use, the thiophene ligand was azeotropically dried with toluene (4 x 10 mL). A solution of ZrBn4 (7.1 mg, 0.0157 mmol, 1.00 equiv) in toluene (0.29 mL) was added dropwise to a clear golden solution of thiophene (21.8 mg, 0.0157 mmol, 1.00 equiv) in anhydrous toluene (2.80 mL) in a nitrogen-filled glove box at 23°C. After stirring (500 rpm) for 30 minutes, the light golden solution was concentrated, and the resulting golden solid was suspended in hexane (3 mL) and concentrated. This suspension / concentration process was repeated two more times, and the resulting complex was suspended in hexane (3 mL), stirred vigorously (1000 rpm) for 2 minutes, filtered through a 0.20 μm PTFE filter, rinsed with hexane (3 x 3 mL), and the hexane filtrate was concentrated to afford the zirconium complex (25.7 mg, 0.0154 mmol, 98%) as a golden solid. NMR indicated the product was present as a mixture of rotamers.

[0347] Only the chemical shifts of the major isomers are listed:

[0348] 1H NMR (400MHz, benzene-d6) δ8.72–8.67(m,2H),8.24(dt,J=2.4,1.2Hz,2H),8.11–8.04(m,2H),7.81(dd,J=2.0,0.6Hz,2H),7. 66(t,J=1.9Hz,2H),7.60(t,J=1.6Hz,2H),7.45–7.24(m,8H),7.05(s,2H),7.04–6.79(m,10H),6.74(td,J=7.2,1.3Hz, 2H),5.85–5.81(m,4H),5.00(dd,J=8.0,1.4Hz,2H),4.19–4.10(m,2H),3.34(d,J=11.8Hz,2H),1.36(s,18H),1.25(s,1 8H), 1.24 (s, 18H), 1.24–1.15 (m, 2H), 1.10 (s, 18H), 0.95–0.91 (m, 2H), 0.61 (d, J = 11.9Hz, 2H), 0.20 (d, J = 11.9Hz, 2H). 13 C NMR (126 MHz, benzene-d6) δ 156.02, 155.85, 150.85, 150.68, 150.40, 147.60, 146.78, 146.28, 139.19, 138.76, 133.45, 131.64, 131.30, 130.64, 130.55, 130.20, 129.62, 129.31, 128 .17,126.10,125.82,125.41,123.61,123.17,121.99,121.58,120.34,120.29,114.84,109.99,72.76,72.01,34.81,34.74,34.6734.63,31.42,31.29,30.75,30.60,25.72.

[0349] Example 46: Synthesis of Primary Catalyst 24

[0350]

[0351] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C., a transparent golden yellow solution of anhydrous C6D6 (1.00 mL) of thiophene (15.6 mg, 0.0112 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.25 mL) solution of HfBn4 (6.1 mg, 0.0112 mmol, 1.00 equivalent). After stirring (500 rpm) for 20 minutes, the light golden yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.009 M C6D6 solution. NMR indicated the product. The same procedure can be used to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration using toluene.

[0352] 1 H NMR (400MHz, benzene-d6) δ8.68(d,J=9.2Hz,2H),8.25(d,J=2.0Hz,2H),8.01(d,J=9.4Hz,2H),7.81(d,J=1.9Hz,2H),7.67(t,J= 1.8Hz,2H),7.61(t,J=1.6Hz,2H),7.39–7.35(m,4H),7.31–7.26(m,4H),7.05(s,2H),7.09–6.85(m,10H),6.76–6.70(m,2 H),5.93–5.86(m,4H),4.95(dd,J=7.9,1.5Hz,2H),4.14(d,J=11.5Hz,2H),3.33(d,J=11.7Hz,2H),1.36(s,18H),1.34–1. 31(m,2H),1.25(s,18H),1.24(s,18H),1.11(s,18H),0.91–0.84(m,2H),0.50(d,J=13.1Hz,2H),-0.09(d,J=13.1Hz,2H). 13C NMR (101 MHz, benzene-d6) δ 156.08, 155.66, 150.85, 150.41, 147.82, 147.64, 146.26, 139.12, 138.79, 133.13, 131.61, 131.32, 130.62, 130.13, 129.42, 129.39, 128.89, 128.13, 127 .97,127.03,127.00,126.91,126.79,126.31,126.25,125.81,125.66,125.59,125.26,115.09,80.70,77.66,34.79,34.73,34.64,34.62,31.40,31.29,30.73,30.59,25.84.

[0353] Example 47: Synthesis of the Boropinacolate Intermediate of Ligand 10

[0354]

[0355] To a pre-cooled solution of t-BuLi (3.2 mL, 5.397 mmol, 3.30 equiv, 1.7 M / pentane) in anhydrous deoxygenated pentane (25 mL) in a nitrogen-filled glove box at -35°C (pre-cooled for 16 hours) was added solid anthracenyl bromide (0.912 g, 1.635 mmol, 1.00 equiv). A pre-cooled solution of pentane / EtO (30 mL, 1:1) was then added dropwise in a rapid fashion while stirring vigorously (1000 rpm). The now golden mixture was placed in a refrigerator (-35°C) for 4 hours before neat i-PrOBPin (1.25 mL, 6.122 mmol, 3.30 equiv) was added to the now reddish-brown mixture via syringe. The now light yellow heterogeneous mixture was stirred at 23° C. for 3 h. i-PrOH (3 mL) was added to neutralize any residual t-BuLi. The mixture was removed from the glove box, water (20 mL) and Et2O (30 mL) were added, and the biphasic mixture was stirred for 2 min, poured into a separatory funnel, and separated. The organics were washed with water (2×25 mL), and the residual organics were extracted with Et2O (2×25 mL). The organics were combined, dried over solid Na2SO4, decanted, and concentrated. The resulting light yellow mixture was suspended in CHCl (20 mL) and filtered through silica gel with CHCl (4×25 mL). The filtrate solution was concentrated to provide anthracenylboropinacolate (0.960 g, 1.588 mmol, 97%) as a light yellow foam. NMR indicated the product.

[0356] 1H NMR (500MHz, chloroform-d) δ8.49 (dd, J=9.1, 0.6Hz, 2H), 7.70 (dd, J=2.1, 0.7Hz, 2H), 7.61 (dd, J=9.2, 2. 1Hz, 2H), 7.56 (t, J = 1.9Hz, 1H), 7.31 (d, J = 1.8Hz, 2H), 1.62 (s, 12H), 1.43 (s, 18H), 1.32 (s, 18H). 13 C NMR (126 MHz, chloroform- d ) δ 150.88, 150.20, 146.33, 140.60, 138.05, 134.05, 129.79, 128.08, 125.82, 124.53, 122.14, 121.98, 121.11, 120.40, 84.15, 35.00, 34.89, 31.66, 30.89, 25.22.

[0357] Example 48: Synthesis of the bromide intermediate of ligand 10

[0358]

[0359] To a pale yellow solution of di-tert-butylanthracene (0.791 g, 1.653 mmol, 1.00 equiv) in CH2Cl2 / MeCN (40 mL, 1:1) was added solid dibromo-dimethylhydantoin (0.250 g, 0.8761 mmol, 0.53 equiv) at 23 ° C. The golden suspension was stirred (500 rpm) for 4 hours, after which TLC indicated complete conversion of the initial anthracene. The solution was concentrated onto celite and purified by silica gel chromatography; bromoanthracene (0.912 g, 1.635 mmol, 99%) was obtained as a white foam using hexane. NMR indicated pure product.

[0360] 1 H NMR (400MHz, chloroform-d) δ8.58(d,J=9.3Hz,2H),7.75(d,J=1.8Hz,2H),7.72(dd,J=9.2,2 .0Hz,2H),7.62(t,J=1.8Hz,1H),7.36(d,J=1.8Hz,2H),1.47(s,18H),1.36(s,18H). 13 C NMR (101 MHz, chloroform-d) δ 150.47, 147.34, 138.56, 137.38, 131.17, 128.66, 127.50, 125.96, 125.88, 122.17, 122.02, 120.74, 35.06, 34.95, 31.68, 30.88.

[0361] Example 49: Synthesis of anthracene intermediate of ligand 10

[0362]

[0363] A mixture of bromoanthracene (0.623 g, 1.687 mmol, 1.00 equiv), Pd(AmPhos)Cl2 (0.119 g, 0.1687 mmol, 0.10 equiv), K3PO4 (1.611 g, 7.590 mmol, 4.50 equiv) and boropinacate (0.800 g, 2.530 mmol, 1.50 equiv) was evacuated and then backfilled with nitrogen four more times before the addition of freshly bubbled deoxygenated 1,4-dioxane (15 mL) and The canary-yellow mixture was stirred for 6 hours in a hood heated to 50°C. After stirring for 6 hours, TLC indicated complete consumption of the initial bromoanthracene. The now purple-black mixture was diluted with CH2Cl2 (20 mL) and suction filtered through a pad of silica gel, rinsing with CH2Cl2 (4×20 mL). The filtrate was concentrated onto celite and purified by silica gel chromatography over hexanes to afford 3,5-di-tert-butylphenyl-bis-tert-butylanthracene (0.791 g, 1.653 mmol, 98%) as a white foam. NMR indicated pure product.

[0364] 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.40 (s, 1H), 8.00 (dd, J = 8.9, 0.6 Hz, 2H), 7.77 (dt, J = 1.8, 0.8 Hz, 2H), 7.60–7.56 (m, 3H), 7.38 (d, J = 1.8 Hz, 2H), 1.46 (s, 18H), 1.36 (s, 18H). 13 CNMR (101 MHz, chloroform-d) δ 150.24, 147.03, 137.89, 137.64, 130.23, 129.88, 128.00, 126.02, 125.01, 124.13, 122.16, 121.44, 120.43, 35.09, 35.04, 31.69, 30.98.

[0365] Example 50: Synthesis of the bromoanthracene intermediate of ligand 10

[0366]

[0367] To a light yellow suspension of di-tert-butylanthracene (1.035 g, 3.563 mmol, 1.00 equiv) in CHCl / MeCN (50 mL, 1:1) was added solid dibromo-dimethylhydantoin (0.510 g, 1.782 mmol, 0.50 equiv) in a small amount at 23°C. The now dark golden suspension was stirred (500 rpm) for 90 minutes, then the mixture was concentrated, suspended in MeOH (30 mL), placed in a mantle heated to 70°C, and stirred vigorously (1000 rpm) for 30 minutes. The golden mixture was then slowly cooled gradually to 23°C, filtered with suction, and the resulting solid washed with MeOH (4 x 10 mL) and dried in vacuo to afford bromo-di-tert-butylanthracene (0.623 g, 1.687 mmol, 47%) as an off-white powder. NMR indicated pure product.

[0368] 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.40 (dt, J = 1.6, 0.7 Hz, 2H), 8.31 (s, 1H), 7.90 (dt, J = 8.9, 0.6 Hz, 2H), 7.56 (dd, J = 8.8, 1.8 Hz, 2H), 1.47 (s, 18H). 13 C NMR (101 MHz, chloroform-d) δ 149.61, 130.53, 130.51, 128.26, 125.81, 124.83, 122.25, 121.90, 35.41, 30.93.

[0369] Example 51: Synthesis of Ligand 11

[0370]

[0371] To a vial equipped with a stir bar was added the dibromide (0.386 g, 0.5418 mmol, 1.00 equiv), K 3 PO 4 (1.035 g, 4.876 mmol, 9.0 equiv), Pd(AmPhos)Cl 2 (78.0 mg, 0.1084 mmol, 0.20 equiv), and mesitylene terphenylboropinacolate (0.716 g, 1.625 mmol, 3.00 equiv). The mixture was evacuated and then backfilled with nitrogen three more times before deoxygenated 1,4-dioxane (6.0 mL) and water (0.6 mL) were added sequentially via syringe. The vial was sealed with a PTFE cap under a nitrogen purge and placed in a hood heated to 50°C. After stirring (1000 rpm) for 36 hours, the purple-black mixture was removed from the hood, gradually cooled to 23 ° C, filtered on a silica gel pad, washed with CH2Cl2 (4 × 20 mL), the transparent purple filtrate was concentrated, and the residual 1,4-dioxane was removed by azeotropic evaporation with toluene (3 × 10 mL). The resulting black mixture was suspended in CH2Cl2 (10 mL), filtered through silica gel to remove residual insoluble impurities, washed with CH2Cl2 (4 × 20 mL), the purple filtrate was concentrated onto diatomaceous earth, and purified by silica gel chromatography using an ISCO chromatography purification system; 25%-65% CH2Cl2 in hexane to obtain protected coupled mesitylene thiophene (0.519 g, 0.4400 mmol, 81%) as a white foam. NMR indicates pure product.

[0372] To a solution of the protected bithiophene in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL). The dark golden brown solution was stirred vigorously (1000 rpm) at 23°C under nitrogen for 24 hours, then diluted with aqueous HCl (25 mL, 1 N) and CHCl (20 mL). The biphasic mixture was poured into a separatory funnel and partitioned. The organics were washed with aqueous HCl (2 x 20 mL, 1 N). The remaining organics were extracted from the aqueous layer with CHCl (2 x 10 mL). The mixture was combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatography purification system; 25%-80% CHCl in hexane to afford the bishydroxythiophene ligand (0.324 g, 0.3047 mmol, 69%, 56% over two steps) as a white foam. NMR indicated pure product.

[0373] 1H NMR (500MHz, chloroform-d) δ7.65(d,J=1.5Hz,4H),7.38(dd,J=7.6,1.7Hz,2H),7.29(ddd,J=8.2,7.4,1.7Hz,2H),7.07(td,J=7.5,1.1Hz,2H),7.03(s ,4H),6.97–6.93(m,8H),6.87(dd,J=8.4,1.1Hz,2H),6.79(t,J=1.5Hz, 2H),4.05–3.97(m,4H),2.33(s,12H),2.10(s,24H),1.92–1.84(m,4H). 13 C NMR (126 MHz, chloroform-d) δ 153.96, 148.35, 141.20, 139.03, 136.44, 135.95, 134.06, 133.00, 131.64, 129.39, 128.20, 128.05, 125.48, 124.72, 122.78, 119.86, 119.56, 113.87, 69.54, 25.82, 21.04, 20.85.

[0374] Characterization of protected ligands:

[0375] 1 H NMR (400MHz, chloroform-d) δ7.51 (d, J=1.6Hz, 4H), 7.41 (dd, J=7.6, 1.8Hz, 2H), 7.2 4–7.18(m,2H),7.16(s,2H),6.97–6.90(m,10H),6.84(t,J=1.6Hz,2H),6.79 (dd,J=8.3,1.1Hz,2H),4.65(s,4H),3.87(m,4H),3.11(q,J=7.0Hz,4H),2. 31 (s, 12H), 2.08 (s, 24H), 1.86 (q, J = 3.2, 2.7Hz, 4H), 0.76 (t, J = 7.0Hz, 6H). 13 C NMR (101 MHz, chloroform-d) δ 156.30, 148.94, 141.53, 138.68, 136.52, 135.74, 133.80, 133.60, 130.90, 129.03, 128.76, 128.06, 127.40, 126.74, 124.47, 121.26, 120.38, 112.31, 96.92, 67.82, 64.79, 25.95, 21.02, 20.78, 14.63.

[0376] Example 52: Synthesis of Main Catalyst 25

[0377]

[0378] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.48 mL) white suspension of thiophene (18.2 mg, 0.0171 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (7.8 mg, 0.0171 mmol, 1.00 equivalent) C6D6 (0.32 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.01 M C6D6 solution. NMR indicates product, and identical procedures can use toluene to prepare the 0.005 M procatalyst solution directly used in polymerization experiments after filtration.

[0379] 1 H NMR(400MHz, benzene-d6)δ8.17(d,J=1.5Hz,4H),7.01–6.93(m,2H),6.90(td,J=7.4,7.0,1.1Hz,2H) ,6.87–6.80(m,6H),6.79–6.75(m,8H),6.74(t,J=1.5Hz,2H),6.70–6.64(m,4H),6.60(s,2H),6 .18–6.12(m,4H),4.38–4.26(m,2H),3.68(d,J=11.5Hz,2H),2.20(s,12H),2.14(s,12H),2.12 (s,12H),1.99(d,J=12.0Hz,2H),1.41(d,J=12.0Hz,2H),0.94–0.81(m,2H),0.47–0.32(m,2H). 13 C NMR (101 MHz, benzene-d6) δ 155.62, 154.42, 147.07, 142.28, 138.70, 136.20, 135.63, 135.47, 135.17, 134.89, 132.27, 130.01, 129.73, 128.89, 128.32, 128.29, 128.13, 127.24, 126.61, 125.44, 125.25, 123.16, 120.79, 119.58, 119.05, 81.18, 74.98, 26.65, 20.98, 20.84, 20.70.

[0380] Example 53: Synthesis of Main Catalyst 26

[0381]

[0382] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.31 mL) white suspension of thiophene (18.5 mg, 0.0174 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to HfBn4 (9.5 mg, 0.0174 mmol, 1.00 equivalent) C6D6 (0.39 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.01 M C6D6 solution. NMR indicated product, and the same procedure can be used to prepare a 0.005 M procatalyst solution directly used in polymerization experiments after filtration using toluene.

[0383] 1 H NMR(400MHz, benzene-d6)δ8.14(d,J=1.5Hz,4H),7.12–7.03(m,2H),6.97–6.93(m,2H),6.93–6.83(m,6H),6 .77(dd,J=8.6,1.6Hz,8H),6.74(t,J=1.5Hz,2H),6.72–6.68(m,2H),6.67–6.62(m,2H),6.60(s,2H),6 .19–6.13(m,4H),4.43–4.33(m,2H),3.73(dd,J=12.7,4.5Hz,2H),2.19(s,12H),2.14(s,12H),2.12(s ,12H),1.82(d,J=12.9Hz,2H),1.19(d,J=12.9Hz,2H),0.89(t,J=10.2Hz,2H),0.36(d,J=11.3Hz,2H). 13 C NMR (101 MHz, benzene-d6) δ 155.44, 154.44, 147.58, 142.26, 138.70, 136.20, 135.48, 135.31, 135.15, 134.78, 132.30, 130.04, 129.75, 128.80, 128.34, 128.28, 128.15, 127.05, 126.95, 126.15, 125.39, 123.35, 120.84, 119.52, 119.50, 81.95, 79.19, 26.70, 20.98, 20.86, 20.70.

[0384] Example 54: Synthesis of the mesitylene-m-terphenyl bromide intermediate of ligand 11

[0385]

[0386] To a solution of tribromobenzene (1.000 g, 3.177 mmol, 1.00 equiv) and Pd(PPh3)4 (0.367 g, 0.3177 mmol, 0.10 equiv) in anhydrous deoxygenated THF (30 mL) in a nitrogen-filled glove box at 23°C was added 2,4,6-trimethylphenylmagnesium bromide solution (8.0 mL, 7.943 mmol, 2.50 equiv, 1.0 M / THF) in a rapid dropwise manner. The resulting red-black solution was placed in a mantle heated to 70° C. and stirred vigorously (1000 rpm) for 18 hours, removed from the mantle, allowed to gradually cool to 23° C., neutralized with i-PrOH (5 mL), removed from the glove box, concentrated, and the resulting dark red-black mixture was suspended in CH2Cl2 (25 mL), suction filtered on a silica gel pad, rinsed with CH2Cl2 (4×25 mL), and the resulting golden brown solution was concentrated onto celite and purified by silica gel chromatography; hexane to give 3,5-bis-(2,4,6-trimethylphenyl)-benzene bromide (0.428 g, 1.088 mmol, 34%) as a white solid. NMR indicated pure product.

[0387] 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.28 (d, J = 1.5 Hz, 2H), 6.93 (s, 4H), 6.87 (d, J = 1.6 Hz, 1H), 2.32 (s, 6H), 2.05 (s, 12H). 13 C NMR (101 MHz, chloroform-d) δ 143.21, 137.47, 136.96, 135.63, 130.43, 129.27, 128.13, 122.41, 21.01, 20.71.

[0388] Example 55: Synthesis of the Boron Pinacolate Intermediate of Ligand 11

[0389]

[0390] To a pre-cooled solution of t-BuLi (10.0 mL, 16.938 mmol, 3.30 equiv., 1.7 M / pentane) in anhydrous deoxygenated pentane (45 mL) in a nitrogen-filled glove box was added dropwise a pre-cooled suspension of mesitylene-m-terphenyl bromide (2.019 g, 5.133 mmol, 1.00 equiv.) in pentane / EtO (30 mL, 1:1) at -35°C (pre-cooled for 16 hours) over 10 minutes. The now golden mixture was placed in the refrigerator (-35°C) for 4 hours before neat i-PrOBPin (3.50 mL, 16.938 mmol, 3.30 equiv.) was added via syringe. The now light yellow heterogeneous mixture was stirred at 23° C. for 3 hours. i-PrOH (3 mL) was added to neutralize any residual t-BuLi. The mixture was removed from the glove box, water (20 mL) and Et2O (30 mL) were added, the biphasic mixture was stirred for 2 minutes, poured into a separatory funnel, separated, and the organics were washed with water (2×25 mL). The residual organics were extracted with Et2O (2×25 mL), combined, dried over solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography on an ISCO; hexanes to 50% CHCl in hexanes to give mesitylene-m-terphenylboropinacolate (2.095 g, 4.757 mmol, 93%) as a white foam. NMR indicated pure product.

[0391] 1 H NMR (500 MHz, chloroform-d) δ 7.58 (dt, J = 2.9, 1.7 Hz, 2H), 7.07 (p, J = 1.8 Hz, 1H), 6.94 (d, J = 2.0 Hz, 4H), 2.34 (s, 6H), 2.07 (s, 12H), 1.37 (s, 12H). 13 C NMR (126 MHz, chloroform-d) δ 140.52, 138.93, 136.27, 135.80, 133.84, 133.10, 127.95, 83.70, 24.98, 21.04, 20.90.

[0392] Example 56: Synthesis of Ligand 12

[0393]

[0394] To a vial equipped with a stir bar was added the dibromide (0.390 g, 0.5476 mmol, 1.00 equiv), K 3 PO 4 (1.046 g, 4.928 mmol, 9.00 equiv), Pd (AmPhos) Cl 2 (78.0 mg, 0.1095 mmol, 0.20 equiv), and TRIP-m-terphenylboropinacolate (1.000 g, 1.643 mmol, 3.00 equiv). The mixture was evacuated and then backfilled with nitrogen three more times before deoxygenated 1,4-dioxane (10.0 mL) and water (1.0 mL) were added sequentially via syringe. The mixture was placed under a nitrogen purge and then placed in a hood heated to 50° C. After stirring (1000 rpm) for 48 hours, the purple-black mixture was removed from the hood, gradually cooled to 23 ° C, diluted with CH2Cl2 (20 mL), filtered with suction on a silica gel pad, washed with CH2Cl2 (4×20 mL), and the transparent purple filtrate was concentrated. The residual 1,4-dioxane was removed by azeotropic evaporation with toluene (3×10 mL). The resulting black mixture was suspended in CH2Cl2 (10 mL), filtered with suction on silica gel to remove residual insoluble impurities, washed with CH2Cl2 (4×20 mL), and the purple filtrate was concentrated onto diatomaceous earth and purified by silica gel chromatography using an ISCO chromatography purification system; 10%-60% CH2Cl2 in hexane to give double-protected coupled thiophene (0.748 g, 0.4928 mmol, 90%) as a golden foam. NMR indicated pure product.

[0395] To a solution of the protected bithiophene in CHCl (10 mL) and 1,4-dioxane (10 mL) was added concentrated HCl (10 mL). The dark golden brown solution was stirred vigorously (1000 rpm) at 23°C under nitrogen for 24 hours, then diluted with aqueous HCl (25 mL, 1 N) and CHCl (20 mL). The biphasic mixture was poured into a separatory funnel and separated. The organics were washed with aqueous HCl (1 x 20 mL, 1 N). The remaining organics were extracted from the aqueous layer with CHCl (2 x 10 mL). The combined organics were dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatography purification system; 10% to 60% CHCl in hexane to afford the bishydroxythiophene ligand (0.610 g, 0.4357 mmol, 88%, 80% over two steps) as a white foam. NMR indicated pure product.

[0396] 1H NMR (400MHz, chloroform-d) δ7.76 (t, J=1.5Hz, 4H), 7.37 (dt, J=7.6, 1.5Hz, 2H), 7.2 8–7.22(m,2H),7.08–7.01(m,14H),6.86(dd,J=4.9,3.3Hz,4H),4.00(d,J= 5.8Hz,4H),2.94(hept,J=6.9Hz,4H),2.88–2.76(m,8H),1.88(d,J=5.3Hz, 4H), 1.31 (d, J = 6.9 Hz, 24H), 1.15 (d, J = 6.9 Hz, 24H), 1.06 (d, J = 6.9 Hz, 24H). 13 C NMR (101 MHz, chloroform-d) δ 153.91, 148.57, 147.69, 146.53, 140.55, 137.04, 133.17, 133.14, 131.69, 129.42, 129.30, 125.49, 124.52, 122.69, 120.44, 119.85, 119.57, 113.59, 69.39, 34.25, 30.41, 25.73, 24.26, 24.24, 24.08.

[0397] Characterization of protected ligands:

[0398] 1 H NMR (400MHz, chloroform-d) δ7.61 (d, J=1.5Hz, 4H), 7.42 (dd, J=7.6, 1.8Hz, 2H), 7.22–7.17 (m, 2H), 7.18 (s, 2H), 7.06(s,8H),6.93(dd,J=15.0,1.0Hz,2H),6.93(d,J=1.3Hz,2H),6.81(dd,J=8.3,1.0Hz,2H),4.68(s,4H ),3.91(d,J=5.4Hz,4H),3.12(q,J=7.0Hz,4H),2.94(p,J=6.9Hz,4H),2.81(p,J=6.8Hz,8H),1.85(q,J=3 .1Hz, 4H), 1.30 (d, J = 7.0Hz, 24H), 1.16 (d, J = 6.8Hz, 24H), 1.07 (d, J = 6.8Hz, 24H), 0.75 (t, J = 7.0Hz, 6H). 13C NMR (101 MHz, chloroform-d) δ 156.28, 148.90, 147.86, 146.43, 140.87, 136.63, 133.81, 132.81, 130.94, 130.18, 128.72, 127.69, 126.85, 124.42, 121.39, 120.46, 120.36, 112.34, 96.83, 67.85, 64.73, 34.27, 30.41, 25.84, 24.42, 24.11, 24.07, 14.55.

[0399] Example 57: Synthesis of Main Catalyst 27

[0400]

[0401] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.10 mL) white suspension of thiophene (9.4 mg, 0.00671 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (3.1 mg, 0.00671 mmol, 1.00 equivalent) C6D6 (0.13 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) directly used in polymerization experiments after filtration.

[0402] 1H NMR (400MHz, benzene-d6) δ8.28(d,J=1.5Hz,4H),7.91(d,J=1.5Hz,2H),7.21–7.11(m,6H),6.99–6.93(m,4H),6.90(td,J=7.5,1.2Hz,2H),6.81–6.67(m ,6H),6.63–6.57(m,2H),6.60(s,2H),6.53(t,J=7.0Hz,2H),6.08–6.02( m,4H),4.34(t,J=10.9Hz,2H),3.80–3.71(m,2H),3.21(p,J=6.8Hz,4H),3 .10(hept,J=6.9Hz,4H),2.98(p,J=6.8Hz,2H),2.92–2.76(m,6H),1.96(d,J=11.7Hz,2H),1.61(d,J=11.8Hz,2H),1.28(d,J=6.9Hz,6H),1.24(dd ,J=6.9,1.7Hz,24H),1.19(ddd,J=9.6,6.7,3.5Hz,24H),1.15(d,J=7.1H z,12H),1.09(d,J=6.8Hz,6H),0.79(t,J=10.1Hz,2H),0.30–0.22(m,2H). 13 C NMR (101 MHz, benzene-d6) δ 155.34, 154.46, 148.27, 148.07, 146.75, 146.59, 146.30, 141.51, 141.39, 137.09, 136.96, 135.89, 134.42, 132.14, 130.57, 130.10, 129.77, 129.25, 128.82, 128.15, 126.78, 1 26.01,125.95,123.22,122.88,120.81,120.69,120.63,120.60,120.33,119.32,81.43,74.81,34.54,34.46,34.43,30.65,30.60,30.51,26.80,25.47,24.37,24.16,24.11,24.02,23.97,23.81.

[0403] Example 58: Synthesis of Primary Catalyst 28

[0404]

[0405] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.0 mL) white suspension of thiophene (18.0 mg, 0.0129 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.28 mL) solution of HfBn4 (7.0 mg, 0.0129 mmol, 1.00 equivalent). After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.01 M C6D6 solution. NMR indicated the product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0406] 1 H NMR (400MHz, benzene-d6) δ8.25(d,J=1.5Hz,4H),8.08(d,J=1.5Hz,2H),7.23–7.11(m,6H),7.08–7.04(m,2H),7.04–6.70(m,10H),6.60( s,2H),6.60–6.52(m,2H),6.51–6.41(m,2H),6.11–6.05(m,2H),5.89(d,J=7.6Hz,2H),4.47–4.34(m,2H),3.80(d,J=12.7Hz,2H),3 .20(p,J=6.9Hz,2H),3.16–2.92(m,6H),2.82(dtt,J=13.7,10.0,6.9Hz,4H),1.78(t,J=12.2Hz,2H),1.35(d,J=12.7Hz,2H),1.32 –1.12(m,54H),1.10(d,J=6.8Hz,6H),0.99(d,J=6.8Hz,6H),0.89(d,J=6.8Hz,6H),0.78(t,J=10.2Hz,2H),0.22(q,J=11.7Hz,2H). 13C NMR (101 MHz, benzene-d6) δ 155.12, 154.44, 153.79, 152.36, 148.13, 148.06, 146.87, 146.71, 146.60, 146.38, 146.28, 146.07, 145.10, 141.51, 136.97, 136.57, 135.56, 134.62, 134.32, 133.63, 132.16, 130.18, 129.79, 128.93, 128.59, 128 .15,126.98,126.41,126.20,125.91,123.40,120.92,120.83,120.69,120.64,120.25,120.12,119.82,82.23,79.41,34.47,34.43,30.82,30.66,30.60,30.54,25.70,25.47,24.54,24.36,24.15,24.03,23.97,23.95,23.83,23.64.

[0407] Example 59: Synthesis of intermediates of ligand 12

[0408]

[0409] To a pre-cooled solution of t-BuLi (10.0 mL, 16.500 mmol, 3.50 equiv, 1.7 M / pentane) in anhydrous deoxygenated pentane (40 mL) in a nitrogen-filled glove box was added a pre-cooled suspension of TRIP-m-terphenyl bromide (2.648 g, 4.714 mmol, 1.00 equiv) in pentane / EtO (30 mL, 1:1) dropwise at -35°C (pre-cooled for 16 hours) over 10 minutes. The now golden mixture was placed in the refrigerator (-35°C) for 4 hours before neat i-PrOBPin (3.40 mL, 16.500 mmol, 3.50 equiv) was added via syringe. The now light yellow heterogeneous mixture was stirred at 23° C. for 3 hours. i-PrOH (3 mL) was added to neutralize the reaction mixture. The mixture was removed from the glove box, water (20 mL) and Et2O (30 mL) were added, and the biphasic mixture was stirred for 2 minutes, poured into a separatory funnel, separated, and the organics washed with water (2×25 mL). The residual organics were extracted with Et2O (2×25 mL), combined, dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography on an ISCO; hexanes to 50% CHCl in hexanes to give TRIP-m-terphenylboropinacolate (1.165 g, 1.914 mmol, 41%) as a white foam. NMR indicated pure product.

[0410] 1 H NMR (500MHz, chloroform-d) δ7.61(d,J=1.7Hz,2H),7.15(t,J=1.8Hz,1H),7.04(s,4H),2.94(p,J=6.9Hz,2H),2.7 3(p,J=6.8Hz,4H),1.34(s,12H),1.31(d,J=6.9Hz,12H),1.16(d,J=6.9Hz,12H),1.05(d,J=6.9Hz,12H). 13 C NMR (126 MHz, chloroform- d ) δ 147.64, 146.47, 139.69, 136.95, 134.16, 133.95, 120.31, 83.60, 34.30, 30.33, 28.85, 25.01, 24.82, 24.48, 24.12, 24.03.

[0411] Example 60: Synthesis of intermediates of ligand 12

[0412]

[0413] To a solution of tribromobenzene (0.500 g, 1.588 mmol, 1.00 equiv) and Pd(PPh3)4 (0.184 g, 0.1588 mmol, 0.10 equiv) in anhydrous deoxygenated THF (10 mL) in a nitrogen-filled glove box at 23°C was added 2,4,6-triisopropylphenylmagnesium bromide solution (8.0 mL, 3.970 mmol, 2.50 equiv, 0.5 M / THF) in a rapid dropwise manner. The resulting red-black solution was placed in a mantle heated to 70° C. and stirred vigorously (1000 rpm) for 24 hours. It was removed from the mantle, allowed to gradually cool to 23° C., neutralized with i-PrOH (5 mL), removed from the glove box, concentrated, and the resulting dark red-black mixture was suspended in CH2Cl2 (25 mL), suction filtered on a silica gel pad, rinsed with CH2Cl2 (4×25 mL), and the resulting golden brown solution was concentrated onto celite and purified by silica gel chromatography; hexane to give 3,5-bis-(2,4,6-isopropylphenyl)-phenyl bromide (0.368 g, 0.6543 mmol, 41%) as a white solid. NMR indicated pure product.

[0414] 1H NMR (500MHz, chloroform-d) δ7.33(d,J=1.4Hz,2H),7.03(s,4H),6.95(t,J=1.5Hz,1H),2.92(hept,J=6.9Hz,2 H), 2.68 (hept, J = 6.9 Hz, 4H), 1.28 (d, J = 6.9 Hz, 12H), 1.15 (d, J = 6.8 Hz, 12H), 1.04 (d, J = 6.9 Hz, 12H). 13 C NMR (126 MHz, chloroform-d) δ 148.32, 146.33, 142.58, 135.39, 130.66, 130.34, 121.88, 120.55, 34.30, 30.44, 24.34, 24.06.

[0415] Example 61: Synthesis of Ligand 13

[0416]

[0417] Before use, the dibromide was azeotropically dried with toluene (4×10 mL). In a nitrogen-filled glove box, a mixture of the dibromide (0.864 g, 1.213 mmol, 1.00 equiv), carbazole (2.043 g, 3.572 mmol, 2.95 equiv), Cu2O (0.868 g, 6.063 mmol, 5.00 equiv) and K2CO3 (3.353 g, 24.260 mmol, 20.0 equiv) in a dried flask equipped with a stirring bar and a reflux condenser was suspended in anhydrous deoxygenated xylene (25.0 mL), and neat N,N'-dimethylethylenediamine (1.30 mL, 11.930 mmol, 10.00 equiv) was added via syringe, and then sealed and mixed under nitrogen. The product was removed from the glove box, placed under nitrogen, and placed in a mantle heated to 140°C with vigorous stirring (1000 rpm) for 72 hours. The dark red heterogeneous mixture was removed from the mantle, allowed to gradually cool to 23°C, diluted with CHCl (30 mL), and vigorously stirred (1000 rpm) for 2 minutes. The mixture was suction filtered over silica gel using CHCl as the eluent, rinsed with CHCl (4 × 25 mL), and the golden-orange filtrate was concentrated onto celite and purified by silica gel chromatography; 10%-45% CHCl in hexanes to give the biscarbazolyl-thiophene (0.384 g, 0.2269 mmol, 19%) as a white foam. NMR indicated the product contained trace impurities. The product was used in subsequent reactions without further purification.

[0418] To a solution of protected hydroxythiophene (0.384 g, 0.2269 mmol, 1.00 equiv) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL) at 23°C under nitrogen. After vigorous stirring (1000 rpm) for 16 hours, the light golden brown solution was diluted with aqueous HCl (20 mL, 1 N) and CHCl (20 mL), poured into a separatory funnel, and separated. The organics were washed with aqueous HCl (1 x 20 mL). The remaining organics were extracted from the aqueous layer with CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography; 10% to 50% CHCl in hexanes to afford hydroxythiophene (0.306 g, 0.1941 mmol, 86%, 16% over two steps) as a light yellow foam. NMR indicated pure product.

[0419] 1 H NMR (400 MHz, chloroform-d) δ 7.91 (d, J = 1.5 Hz, 4H), 7.55 (dd, J = 7.6, 1.8 Hz, 2H), 7.46 (d, J = 8.3 Hz, 4H), 7.28–7.21 (m, 8H), 7.16–7.09 (m, 10H), 7.00 (s, 2H), 6.95 (dd, J = 8.3, 1.1 Hz, 2 H),4.15(d,J=5.1Hz,4H),3.01(hept,J=6.9Hz,4H),2.79(hept,J=7.0Hz,8H),2.03(h , J=2.7Hz, 4H), 1.38 (d, J=6.9Hz, 24H), 1.13 (d, J=5.9Hz, 36H), 1.06 (d, J=6.8Hz, 12H). 13 C NMR (101 MHz, chloroform-d) δ 154.20, 148.01, 147.75, 147.15, 141.02, 137.48, 132.93, 131.44, 130.77, 129.69, 128.24, 124.53, 123.29, 122.98, 121.15, 120.56, 119.59, 115.23, 113.97, 109.84, 69.79, 34.35, 30.27, 26.03, 24.36, 24.18.

[0420] Characterization of protected ligands:

[0421] 1H NMR (400MHz, chloroform-d) δ7.84(s,4H),7.55(t,J=6.8Hz,6H),7.37(s,2H),7.28(dd,J=8.3,1.5Hz,4H ),7.26–7.20(m,2H),7.10(d,J=3.3Hz,8H),7.00(t,J=7.5Hz,2H),6.95(d,J=8.3Hz,2H),4.62(s ,4H),4.12(d,J=5.2Hz,4H),2.97(hept,J=6.9Hz,4H),2.84(q,J=7.0Hz,4H),2.74(h,J=6.9Hz,8 H), 2.07 (d, J = 5.0Hz, 4H), 1.34 (d, J = 6.9Hz, 24H), 1.09 (d, J = 6.9Hz, 48H), 0.54 (t, J = 7.0Hz, 6H). 13 C NMR (101 MHz, chloroform-d) δ 156.44, 148.84, 147.72, 147.15, 146.97, 140.95, 137.42, 132.92, 132.03, 130.91, 129.16, 128.30, 123.98, 123.21, 122.69, 120.92, 120.58, 120.57, 120.51, 112.36, 110.12, 97.06, 34.29, 30.24, 26.17, 24.38, 24.31, 24.29, 24.12, 14.11.

[0422] Example 62: Synthesis of Primary Catalyst 29

[0423]

[0424] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.0 mL) transparent colorless solution of thiophene (20.0 mg, 0.0127 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (5.8 mg, 0.0127 mmol, 1.00 equivalent) C6D6 (0.24 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.01 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) directly used in polymerization experiments after filtration.

[0425] 1H NMR (400MHz, benzene-d6) δ8.09(d,J=1.5Hz,2H),7.97(d,J=1.2Hz,2H),7.75(d,J=8.3Hz,2H),7.41–7.35(m,4H),7 .25–7.12(m,10H),6.97–6.94(m,4H),6.85–6.75(m,6H),6.62(s,2H),6.61–6.55(m,2H),6.12–6.05(m,4H),5 .89(dd,J=8.0,1.4Hz,2H),4.13(t,J=10.2Hz,2H),3.42(d,J=11.5Hz,2H),3.09–2.69(m,12H),1.86(d,J=11. 8Hz,2H),1.38–0.97(m,62H),0.97–0.88(m,6H),0.85(d,J=6.8Hz,6H),0.89–0.80(m,2H),0.76–0.65(m,2H). 13 C NMR (101 MHz, benzene-d6) δ 155.12, 152.04, 148.20, 148.08, 147.83, 147.70, 147.66, 147.09, 146.69, 146.51, 140.61, 140.33, 137.84, 137.67, 133.67, 133.26, 133.00, 128.84, 128.15, 126.38, 124.55, 122.75, 122.54, 121. 41,121.13,120.79,120.75,120.50,120.44,120.35,120.10,117.19,115.44,112.27,108.98,79.88,75.02,34.57,34.48,30.54,30.49,30.43,30.34,25.91,24.78,24.29,24.27,24.24,24.11,24.08,24.04,24.02.

[0426] Example 63: Synthesis of Primary Catalyst 30

[0427]

[0428] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C., a transparent, colorless solution of anhydrous C6D6 (1.0 mL) of thiophene (20.0 mg, 0.0127 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.28 mL) solution of HfBn4 (6.9 mg, 0.0127 mmol, 1.00 equivalent). After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.01 M C6D6 solution. NMR indicated the product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0429] 1 H NMR(400MHz, benzene-d6)δ8.11(dd,J=1.7,0.6Hz,2H),8.01–7.98(m,2H),7.75–7.71(m ,2H),7.42–7.32(m,6H),7.26(s,4H),7.16(dd,J=7.4,2.0Hz,4H),7.11(dd,J=5.3 ,2.4Hz,2H),6.98–6.93(m,2H),6.91–6.74(m,6H),6.61(s,2H),6.59–6.54(m,2H) ,6.18–6.12(m,4H),5.82(dd,J=7.9,1.6Hz,2H),4.23(t,J=10.7Hz,2H),3.44(d,J =11.2Hz,2H),3.09–2.68(m,12H),1.78(d,J=13.0Hz,2H),1.29(dt,J=6.8,1.9Hz, 18H),1.19(ddd,J=7.1,3.6,2.0Hz,18H),1.17–1.14(m,6H),1.14–1.11(m,6H),1. 09(dd,J=7.0,1.9Hz,6H),1.06(d,J=6.8Hz,6H),0.94(d,J=6.8Hz,6H),0.86(d,J= 6.9Hz, 6H), 0.78 (d, J = 8.5Hz, 2H), 0.72 (d, J = 13.1Hz, 2H), 0.61 (d, J = 13.2Hz, 2H). 13C NMR (101 MHz, benzene-d6) δ 155.15, 151.90, 148.22, 147.82, 147.72, 147.60, 147.09, 146.58, 140.43, 140.12, 137.87, 137.66, 133.67, 133.24, 132.70, 131.67, 130.15, 129.85, 129.35, 129.02, 128.54, 128.15, 127.14, 126.61, 126.55, 126.18, 124.54, 124 .32,123.30,122.60,121.36,121.06,120.79,120.75,120.52,120.33,120.08,116.92,116.04,112.43,108.83,81.55,79.59,34.57,34.48,30.54,30.42,30.33,26.26,24.79,24.42,24.36,24.32,24.29,24.26,24.10,24.08,24.04,23.97,23.91.

[0430] Example 64: Synthesis of an intermediate of ligand 13

[0431]

[0432] To a solution of 3,6-dibromocarbazole (2.000 g, 6.154 mmol, 1.00 equiv) and Pd(PPh3)4 (0.711 g, 0.6155 mmol, 0.10 equiv) in anhydrous deoxygenated THF (30 mL) in a nitrogen-filled glove box was added 2,4,6-triisopropylphenylmagnesium bromide solution (39.4 mL, 19.693 mmol, 3.30 equiv, 0.5 M / THF) in a rapid dropwise manner. The now golden solution was placed in a mantle heated to 70°C and stirred (500 rpm) for 48 hours. The resulting black solution was removed from the mantle, allowed to gradually cool to 23°C, neutralized with i-PrOH (10 mL), stirred for 2 minutes, removed from the glove box, diluted with CHCl (20 mL), filtered through a pad of silica gel with suction, rinsed with CHCl (4 x 20 mL), and the filtrate solution was concentrated onto Celite and purified by silica gel chromatography; hexane to 25% CHCl in hexane to give the disubstituted carbazole (2.041 g, 3.569 mmol, 58%) as a white solid. NMR indicated pure product.

[0433] 1H NMR (500MHz, chloroform-d) δ8.14(s,1H),7.86–7.81(m,2H),7.49(dd,J=8.2,0.7Hz,2H),7.29–7.23(m,2H),7.10( s, 4H), 2.98 (hept, J = 6.9Hz, 2H), 2.75 (hept, J = 6.9Hz, 4H), 1.34 (d, J = 7.0Hz, 12H), 1.10 (d, J = 6.9Hz, 24H). 13 C NMR (126 MHz, chloroform- d ) δ 147.64, 147.14, 138.58, 137.56, 131.93, 128.06, 123.04, 121.14, 120.52, 110.02, 34.28, 30.25, 24.35, 24.26, 24.12.

[0434] Example 65: Synthesis of Ligand 14

[0435]

[0436] Before use, the dibromide was azeotropically dried with toluene (4×10 mL). In a nitrogen-filled glove box, a mixture of the dibromide (0.864 g, 1.213 mmol, 1.00 equiv), carbazole (1.512 g, 3.747 mmol, 3.10 equiv), Cu2O (0.868 g, 6.063 mmol, 5.00 equiv) and K2CO3 (3.353 g, 24.260 mmol, 20.0 equiv) in a dried flask equipped with a stirring bar and a reflux condenser was suspended in anhydrous deoxygenated xylene (25.0 mL), and neat N,N'-dimethylethylenediamine (1.30 mL, 11.930 mmol, 10.00 equiv) was added via syringe, and then the mixture was sealed under nitrogen and mixed. The product was removed from the glove box, placed under nitrogen, and placed in a mantle heated to 140°C with vigorous stirring (1000 rpm) for 72 hours. The dark red heterogeneous mixture was removed from the mantle, allowed to gradually cool to 23°C, diluted with CHCl (30 mL), and vigorously stirred (1000 rpm) for 2 minutes. The mixture was suction filtered over silica gel using CHCl as the eluent, rinsed with CHCl (4 × 25 mL), and the golden-orange filtrate was concentrated onto celite and purified by silica gel chromatography; 10%-50% CHCl in hexanes to give the biscarbazolyl-thiophene (0.167 g, 0.1230 mmol, 11%) as a white foam. NMR indicated the product contained a small amount of impurities. The product was used in subsequent reactions without further purification.

[0437] To a solution of protected hydroxythiophene (0.167 g, 0.1230 mmol, 1.00 equiv) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL) at 23°C under nitrogen. After vigorous stirring (1000 rpm) for 16 hours, the light golden brown solution was diluted with aqueous HCl (20 mL, 1 N) and CHCl (20 mL), poured into a separatory funnel, and separated. The organics were washed with aqueous HCl (1 x 20 mL). The remaining organics were extracted from the aqueous layer with CHCl (2 x 20 mL). The combined organics were dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography; 10% to 50% CHCl in hexanes to afford hydroxythiophene (0.129 g, 0.1039 mmol, 85%, 9% over two steps) as a light yellow foam. NMR indicated pure product.

[0438] 1 H NMR (400MHz, chloroform-d) δ7.79 (s, 4H), 7.44 (dd, J=8.0, 4.6Hz, 6H), 7.30 (td, J=7 .9,1.8Hz,2H),7.15(td,J=7.5,1.0Hz,2H),7.10(s,2H),7.05(dd,J=8.3,1. 6Hz,4H),7.00(s,4H),6.96–6.92(m,2H),6.91(s,4H),6.76(s,2H),4.10–4. 04(m,4H),2.38(s,12H),2.06(s,12H),2.00(t,J=3.4Hz,4H),1.91(s,12H). 13 C NMR (101 MHz, chloroform-d) δ 154.07, 148.15, 141.09, 139.57, 136.65, 136.28, 133.18, 131.44, 130.59, 129.55, 128.01, 128.00–127.92 (m), 127.43, 124.49, 123.68, 123.02, 120.70, 119.97, 115.04, 113.89, 110.25, 70.12, 26.36, 21.07, 20.93.

[0439] Characterization of protected ligands:

[0440] 1H NMR (400MHz, chloroform-d) δ7.81(s,4H),7.55(dd,J=8.4,4.0Hz,6H),7.31(s,2H),7.24(dt,J=13.7,8.0Hz,6H),7.05–6.92(m,12H),4.58(s, 4H), 4.13 (d, J = 4.8Hz, 4H), 2.84 (q, J = 7.0Hz, 4H), 2.37 (s, 12H), 2.10–2.05 (m, 4H), 2.07 (s, 12H), 2.05 (s, 12H), 0.55 (t, J = 7.0Hz, 6H).

[0441] Example 66: Synthesis of Main Catalyst 31

[0442]

[0443] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (0.77 mL) transparent colorless solution of thiophene (11.0 mg, 0.00885 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (4.1 mg, 0.00885 mmol, 1.00 equivalent) C6D6 (0.17 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.01 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) directly used in polymerization experiments after filtration.

[0444] 1H NMR (400MHz, benzene-d6) δ7.93(dd,J=1.6,0.7Hz,2H),7.79–7.74(m,4H),7.50–7.45(m,2H),7.41(dd,J=8.4,0.7Hz,2H),7.33–7.22(m,4H), 6.95(dddt,J=5.9,2.1,1.4,0.7Hz,6H),6.93–6.87(m,2H),6.87–6.83(m,6H),6.81–6.76(m,2H),6.70–6.63(m,2H),6.62(s,2H),6.12 (dd,J=8.3,1.3Hz,4H),5.75(dd,J=8.3,1.2Hz,2H),4.20(t,J=10.6Hz,2H),3.45(d,J=12.5Hz,2H),2.23(s,6H),2.21(s,6H),2.14(s, 6H), 2.11 (s, 6H), 2.10 (s, 6H), 1.88 (s, 6H), 1.72 (d, J = 12.2Hz, 2H), 0.90 (d, J = 12.2Hz, 2H), 0.87–0.74 (m, 2H), 0.64 (d, J = 13.0Hz, 2H). 13 C NMR (101 MHz, benzene-d6) δ 155.52, 151.75, 146.75, 140.31, 139.99, 139.56, 139.44, 136.69, 136.55, 136.26, 135.84, 135.80, 135.58, 134.03, 133.62, 133.10, 130.53, 130.35, 1 28.94,128.44,128.25,126.26,124.92,123.10,121.39,120.94,120.54,116.94,115.57,112.75,109.22,80.80,76.08,26.15,21.37,21.02,21.00,20.91,20.81,20.72.

[0445] Example 67: Synthesis of Primary Catalyst 32

[0446]

[0447] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C., a transparent, colorless solution of anhydrous C6D6 (0.83 mL) of thiophene (15.2 mg, 0.0122 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.29 mL) solution of HfBn4 (6.7 mg, 0.0122 mmol, 1.00 equivalent). After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.01 M C6D6 solution. NMR indicated the product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0448] 1 H NMR (400MHz, benzene-d6) δ7.94(dd,J=1.6,0.6Hz,2H),7.79(t,J=1.1Hz,2H),7.75(dd,J=8.2,0.7Hz,2H),7.32(d,J=0.8Hz,2H),7.31(d,J=1.5Hz,2H),7.2 6–7.23(m,2H),6.96(tdd,J=3.6,1.4,0.7Hz,6H),6.90(tt,J=7.5,2.3Hz,4 H),6.87–6.83(m,2H),6.79(td,J=7.6,1.2Hz,2H),6.70–6.64(m,2H),6.62 (s,2H),6.63–6.58(m,4H),6.13(dd,J=8.2,1.3Hz,4H),5.75(dd,J=8.3,1. 2Hz,2H),4.27(t,J=10.7Hz,2H),3.57–3.44(m,2H),2.23(s,6H),2.21(s,6 H),2.14(s,6H),2.11(s,6H),2.10(s,6H),1.89(s,6H),1.55(d,J=13.2Hz, 2H), 0.79 (q, J=9.4, 8.8Hz, 2H), 0.64 (d, J=13.2Hz, 2H), 0.60–0.50 (m, 2H). 13CNMR (101 MHz, benzene-d6) δ 155.43, 151.81, 147.43, 140.20, 139.91, 139.58, 139.44, 137.46, 136.74, 136.57, 136.27, 135.55, 134.04, 133.61, 132.77, 131.69, 130.41, 129.85, 129.00, 128.54, 128.45, 128. 27,128.07,127.06,126.80,126.58,126.22,125.26,124.92,123.34,123.02,121.38,120.96,120.47,116.82,116.02,112.81,109.15,81.81,79.70,26.36,21.39,21.05,21.00,20.90,20.81,20.72.

[0449] Example 68: Synthesis of intermediates of ligand 14

[0450]

[0451] A mixture of carbazole (2.000 g, 6.154 mmol, 1.00 equiv), 2,4,6-trimethylphenylboronic acid (6.056 g, 36.923 mmol, 6.00 equiv), Pd(PPh3)4 (1.422 g, 1.231 mmol, 0.20 equiv) and K2CO3 (15.309 g, 110.8 mmol, 18.0 equiv) equipped with a reflux condenser was evacuated and then backfilled with nitrogen. This evacuation / refilling process was repeated three more times. Freshly deoxygenated 1, 4-Dioxane (70 mL) and H₂O (7.0 mL) were added to the golden mixture, which was placed in a mantle heated to 100°C and stirred vigorously (1000 rpm) for 48 hours. The mixture was removed from the mantle and allowed to gradually cool to 23°C. The golden suspension was suction filtered through silica gel, rinsed with CHCl (4 x 20 mL). The yellow filtrate was concentrated onto Celite and purified by silica gel chromatography; hexane-50% CHCl in hexane to afford the disubstituted carbazole (1.542 g, 3.821 mmol, 62%) as a white foam. NMR indicated pure product.

[0452] 1 H NMR (500 MHz, CHLOROFORM-d) δ 8.04 (s, 1H), 7.90–7.86 (m, 2H), 7.53 (dd, J = 8.2, 0.7 Hz, 2H), 7.28 (dd, J = 8.2, 1.6 Hz, 2H), 7.08 (s, 4H), 2.45 (s, 6H), 2.15 (s, 12H).13 C NMR (126 MHz, chloroform-d) δ 139.73, 138.67, 136.76, 136.44, 132.36, 128.13, 127.48, 123.56, 120.85, 110.66, 21.16, 21.12.

[0453] Example 69: Synthesis of Ligand 15

[0454]

[0455] Before use, the dibromide was azeotropically dried with toluene (4×10 mL). In a nitrogen-filled glove box, a mixture of the dibromide (0.864 g, 1.213 mmol, 1.00 equiv), carbazole (1.557 g, 2.863 mmol, 2.36 equiv), Cu2O (0.868 g, 6.063 mmol, 5.00 equiv) and K2CO3 (3.353 g, 24.260 mmol, 20.0 equiv) in a dried flask equipped with a stirring bar and a reflux condenser was suspended in anhydrous deoxygenated xylene (25.0 mL), and neat N,N'-dimethylethylenediamine (1.30 mL, 11.930 mmol, 10.00 equiv) was added via syringe, and then sealed and mixed under nitrogen. The product was removed from the glove box, placed under nitrogen, and placed in a mantle heated to 140°C with vigorous stirring (1000 rpm) for 72 hours. The dark red heterogeneous mixture was removed from the mantle, allowed to gradually cool to 23°C, diluted with CHCl (30 mL), and vigorously stirred (1000 rpm) for 2 minutes. The mixture was suction filtered over silica gel using CHCl as the eluent, rinsed with CHCl (4 × 25 mL), and the golden-orange filtrate was concentrated onto celite and purified by silica gel chromatography; 10%-50% CHCl in hexanes to give biscarbazolyl-thiophene (0.560 g, 0.3418 mmol, 28%) as a white foam. NMR indicated product. The product was used in subsequent reactions without further purification.

[0456] To a solution of protected hydroxythiophene (0.560 g, 0.3418 mmol, 1.00 equiv) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL) at 23°C under nitrogen. After vigorous stirring (1000 rpm) for 16 hours, the light golden brown solution was diluted with aqueous HCl (20 mL, 1 N) and CHCl (20 mL), poured into a separatory funnel, and separated. The organics were washed with aqueous HCl (1 x 20 mL). The remaining organics were extracted from the aqueous layer with CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography; 10%-50% CHCl in hexanes to afford hydroxythiophene (0.461 g, 0.3029 mmol, 89%, 25% over two steps) as a light yellow foam. NMR indicated pure product.

[0457] 1 H NMR (400MHz, chloroform-d) δ8.32 (d, J=1.6Hz, 4H), 7.61 (dd, J=8.5, 1.7Hz, 4H), 7.53 –7.47(m,10H),7.44(t,J=1.8Hz,4H),7.41(d,J=8.4Hz,4H),7.18(s,2H),7. 10(td,J=7.8,1.9Hz,2H),7.04(td,J=7.5,1.2Hz,2H),6.90(s,2H),6.79(dd ,J=8.1,1.2Hz,2H),4.03(d,J=4.9Hz,4H),1.94–1.84(m,4H),1.41(s,72H). 13 C NMR (101 MHz, chloroform-d) δ 154.06, 151.03, 148.00, 141.74, 141.55, 135.48, 131.26, 130.87, 129.70, 126.14, 124.23, 124.10, 122.73, 122.07, 120.80, 119.45, 119.24, 115.02, 113.51, 110.45, 69.56, 34.99, 31.59, 25.98.

[0458] Characterization of protected ligands:

[0459] 1H NMR (400MHz, chloroform-d) δ8.40(s,4H),7.79–7.71(m,4H),7.65–7.41(m,20H),7.28(t,J=7.8Hz,2H),7.05(q,J=8.3,7.9Hz, 4H), 4.62 (s, 4H), 4.21 (d, J = 5.2Hz, 4H), 2.92 (q, J = 7.0Hz, 4H), 2.21-2.11 (m, 4H), 1.49 (s, 72H), 0.62 (t, J = 7.0Hz, 6H). 13 C NMR (101 MHz, chloroform-d) δ 156.55, 151.12, 149.20, 141.73, 141.55, 135.72, 132.23, 131.04, 129.27, 126.40, 124.12, 122.11, 121.74, 120.93, 120.77, 120.59, 119.17, 112.34, 110.87, 96.83, 68.21, 64.56, 35.07, 31.68, 26.33, 14.29.

[0460] Example 70: Synthesis of Main Catalyst 33

[0461]

[0462] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.75 mL) transparent colorless solution of thiophene (14.9 mg, 0.00979 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (4.5 mg, 0.00979 mmol, 1.00 equivalent) C6D6 (0.19 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) directly used in polymerization experiments after filtration.

[0463] 1H NMR (400MHz, benzene-d6) δ8.56(dd,J=1.7,0.7Hz,2H),8.10(dd,J=1.8,0.6Hz,2H),7.78(d,J=1.8Hz,4H),7.77–7.70(m,4H),7.65(dd,J=8.5,1.7Hz ,2H),7.60(t,J=1.8Hz,2H),7.53(d,J=1.8Hz,4H),7.47(t,J=1.8Hz,2H),7.34(dd,J=8.4,0.6Hz,2H),7.13(dd,J=7.7,1.8Hz,2H),7.01–6.96( m,4H),6.94–6.89(m,2H),6.73(dddd,J=7.4,6.1,5.1,1.2Hz,4H),6.67(s,2H),6.17–6.09(m,4H),5.19(dd,J=8.3,1.1Hz,2H),4.09(t,J=10. 5Hz,2H),3.50–3.37(m,2H),1.38(s,36H),1.33(s,36H),1.02(d,J=12. 1Hz, 2H), 0.89–0.76 (m, 2H), 0.73–0.60 (m, 2H), 0.54 (d, J = 12.1Hz, 2H). 13 C NMR (101 MHz, benzene-d6) δ 155.92, 152.28, 151.21, 150.56, 146.08, 142.48, 142.00, 141.42, 141.01, 136.51, 135.85, 133.02, 131.32, 130.44, 128.74, 128.15, 126.92, 125.90, 125.5 5,125.26,123.49,123.30,122.67,122.36,120.98,120.58,120.08,119.62,119.34,117.07,115.30,112.77,110.05,80.79,74.27,34.79,34.66,31.43,31.40,31.37,25.86.

[0464] Example 71: Synthesis of Primary Catalyst 34

[0465]

[0466] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, a transparent, colorless solution of anhydrous C6D6 (1.84 mL) of thiophene (15.9 mg, 0.0105 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.25 mL) solution of HfBn4 (5.7 mg, 0.0105 mmol, 1.00 equivalent). After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.005 M C6D6 solution. NMR indicated the product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0467] 1 H NMR (400MHz, benzene-d6) δ8.61–8.55(m,2H),8.10(d,J=1.6Hz,2H),7.78(d,J=1.8Hz,4H),7.76–7.67(m,4H),7.65–7.58(m,4H),7.53(d ,J=1.8Hz,4H),7.47(t,J=1.8Hz,2H),7.26(d,J=8.6Hz,2H),7.13(dd,J=7.7,1.8Hz,2H),7.05–6.99(m,2H),6.98–6.90(m,4H),6.7 4(td,J=7.5,1.1Hz,2H),6.72–6.68(m,2H),6.67(s,2H),6.20–6.12(m,4H),5.21–5.15(m,2H),4.11(t,J=10.8Hz,2H),3.48(d,J= 9.3Hz, 2H), 1.38 (s, 36H), 1.34 (s, 36H), 0.91 (d, J = 13.2Hz, 2H), 0.87–0.73 (m, 2H), 0.57 (d, J = 13.0Hz, 2H), 0.28 (d, J = 13.2Hz, 2H). 13CNMR (101MHz, benzene-d6) δ155.72,152.33,151.21,150.55,147.05,142.51,142.00,141.35,140.99,136.54,135.86,132.67,131.36,130.50,128.81,128.15,127.13,127.08,126.15,1 25.62,125.33,125.26,123.83,123.23,122.69,122.35,120.92,120.58,120.05,119.58,119.29,116.96,115.76,112.85,110.06,81.80,78.41,34.79,34.66,31.45,31.40,26.05.

[0468] Example 72: Synthesis of intermediates of ligand 15

[0469]

[0470] A mixture of carbazole (1.062 g, 3.267 mmol, 1.00 equiv), 3,5-di-tert-butylphenylboropinacol (3.100 g, 9.801 mmol, 3.00 equiv), Pd(PPh3)4 (0.755 g, 0.6534 mmol, 0.20 equiv) and K3PO4 (6.241 g, 29.403 mmol, 9.00 equiv) equipped with a reflux condenser was evacuated and then backfilled with nitrogen. This evacuation / refilling process was repeated three more times. Freshly deoxygenated 1 The golden mixture was placed in a mantle heated to 100°C and stirred vigorously (1000 rpm) for 48 hours. The mixture was removed from the mantle and allowed to gradually cool to 23°C. The golden suspension was filtered through silica gel with suction, rinsed with CH2Cl2 (4×20 mL). The yellow filtrate was concentrated onto celite and purified by silica gel chromatography; hexane-50% CH2Cl2 in hexane to give the disubstituted carbazole (1.551 g, 2.852 mmol, 87%) as a white foam. NMR indicated pure product.

[0471] 1 H NMR (500 MHz, CHLOROFORM-d) δ 8.34–8.29 (m, 2H), 8.10 (s, 1H), 7.68 (dd, J = 8.4, 1.8 Hz, 2H), 7.54 (d, J = 1.7 Hz, 4H), 7.51 (d, J = 8.3 Hz, 2H), 7.45 (t, J = 1.8 Hz, 2H), 1.43 (s, 36H). 13C NMR (126 MHz, chloroform-d) δ 151.03, 141.57, 139.25, 134.55, 126.04, 123.93, 122.02, 120.74, 119.18, 110.71, 35.01, 31.60.

[0472] Example 73: Synthesis of Ligand 16

[0473]

[0474] Before use, the dibromide was azeotropically dried with toluene (4×10 mL). In a nitrogen-filled glove box, a mixture of the dibromide (2.054 g, 2.192 mmol, 1.00 equiv), carbazole (3.063 g, 10.961 mmol, 5.00 equiv), Cu2O (1.568 g, 10.961 mmol, 5.00 equiv) and K2CO3 (6.059 g, 43.844 mmol, 20.0 equiv) in an oven-dried flask equipped with a stirring bar and a reflux condenser was suspended in anhydrous deoxygenated xylene (50.0 mL). Neat N,N'-dimethylethylenediamine (2.40 mL, 21.922 mmol, 10.00 equiv) was added via syringe, and the mixture was sealed under nitrogen. The mixture was removed from the glove box, placed under nitrogen, and placed in a mantle heated to 140°C with vigorous stirring (1000 rpm) for 72 hours. The dark red heterogeneous mixture was removed from the mantle, allowed to gradually cool to 23°C, diluted with CHCl (30 mL), and vigorously stirred (1000 rpm) for 2 minutes. The mixture was suction filtered over silica gel using CHCl as the eluent, rinsed with CHCl (4 × 25 mL), and the golden-orange filtrate was concentrated onto celite and purified by silica gel chromatography; 10%-50% CHCl in hexanes to give biscarbazolyl-thiophene (0.830 g, 0.6222 mmol, 28%) as a white foam. NMR indicated product. The product was used in subsequent reactions without further purification.

[0475] To a solution of protected hydroxythiophene (0.830 g, 0.6222 mmol, 1.00 equiv) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL) at 23°C under nitrogen. After vigorous stirring (1000 rpm) for 16 hours, the light golden brown solution was diluted with aqueous HCl (20 mL, 1 N) and CHCl (20 mL), poured into a separatory funnel, and separated. The organics were washed with aqueous HCl (1 x 20 mL). The remaining organics were extracted from the aqueous layer with CHCl (2 x 20 mL). The combined organics were dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography; 10% to 50% CHCl in hexanes to afford hydroxythiophene (0.461 g, 0.4796 mmol, 77%, 22% over two steps) as a light yellow foam. NMR indicated pure product.

[0476] 1 H NMR (500MHz, chloroform-d) δ8.16(dd,J=1.9,0.6Hz,4H),7.56(d,J=2.5Hz,2H),7.48(dd,J=8.6,1.9Hz,4H),7.35–7.30(m,6H),7.24(s,2H),6.97 (s, 2H), 6.83 (d, J = 8.6Hz, 2H), 4.06 (d, J = 4.2Hz, 4H), 1.92 (q, J = 2.7, 1.9Hz, 4H), 1.81 (s, 4H), 1.49 (s, 36H), 1.45 (s, 12H), 0.82 (s, 18H). 13 C NMR (126 MHz, chloroform-d) δ 151.86, 147.93, 144.50, 143.11, 140.51, 131.44, 129.16, 127.22, 123.64, 123.53, 123.47, 119.02, 116.32, 115.57, 112.79, 109.73, 69.54, 56.98, 38.22, 34.78, 32.48, 32.11, 31.98, 31.71, 26.15.

[0477] Characterization of protected ligands:

[0478] 1H NMR (400MHz, chloroform-d) δ8.11(d,J=1.9Hz,4H),7.53–7.46(m,6H),7.39(d,J=8.6Hz,4H),7.33–7.26(m,4H),6.91(d,J=8.6Hz,2H),4.51(s,4H) ,4.12(d,J=4.7Hz,4H),2.80(q,J=7.0Hz,4H),2.07(s,4H),1.77(s,4H),1.47(s,36H),1.41(s,12H),0.79(s,18H),0.50(t,J=7.0Hz,6H). 13 C NMR (101 MHz, chloroform-d) δ 154.30, 148.90, 143.23, 142.07, 140.55, 132.68, 128.72, 126.67, 123.79, 123.47, 123.42, 121.90, 120.33, 116.05, 111.56, 110.08, 96.36, 68.23, 64.38, 56.98, 38.06, 34.74, 32.41, 32.06, 31.90, 31.71, 26.45, 14.13.

[0479] Example 74: Synthesis of Primary Catalyst 35

[0480]

[0481] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (2.26 mL) transparent colorless solution of thiophene (15.2 mg, 0.0125 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (5.7 mg, 0.0125 mmol, 1.00 equivalent) C6D6 (0.24 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) directly used in polymerization experiments after filtration.

[0482] 1H NMR (500MHz, benzene-d6) δ8.52(dd,J=2.0,0.6Hz,2H),8.12(dd,J=2.0,0.6Hz,2H),7.74(dd,J=8.5,0.6Hz,2H),7.53(dd,J=8.5,1.9Hz,2H),7.46–7 .40(m,4H),7.25(dd,J=8.7,0.6Hz,2H),7.12–7.00(m,2H),6.99–6.95 (m,4H),6.84(tt,J=7.2,1.3Hz,2H),6.75(s,2H),6.13–6.09(m,4H),5. 22(d,J=8.7Hz,2H),4.13(t,J=10.8Hz,2H),3.47(dd,J=12.2,4.6Hz,2H),1.66(d,J=14.6Hz,2H),1.57(s,18H),1.51(d,J=14.6Hz,3H),1.23( s,18H),1.20(s,6H),1.14(s,6H),1.01(d,J=12.1Hz,2H),0.92(d,J=5.4Hz,2H),0.72(s,18H),0.67(d,J=5.4Hz,2H),0.50(d,J=12.4Hz,2H). 13 C NMR (126 MHz, benzene-d6) δ 153.70, 151.82, 148.69, 146.79, 143.19, 142.99, 139.97, 139.55, 133.73, 128.21, 127.28, 126.81, 125.32, 124.96, 122.86, 122.68 ,122.63,120.61,116.40,116.35,115.96,115.88,112.43,109.47,80.91,74.39,56.60,38.21,34.68,34.37,32.17,32.08,31.68,31.65,30.10,25.85.

[0483] Example 75: Synthesis of Primary Catalyst 36

[0484]

[0485] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, a transparent, colorless solution of anhydrous C6D6 (2.54 mL) of thiophene (17.5 mg, 0.0144 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.33 mL) solution of HfBn4 (7.8 mg, 0.0144 mmol, 1.00 equivalent). After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.005 M C6D6 solution. NMR indicated the product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0486] 1 H NMR (500MHz, benzene-d6) δ8.54(dd,J=2.0,0.6Hz,2H),8.13(dd,J=2.0,0.6Hz,2H),7.72(dd,J=8.5,0.6Hz,2H),7.53(dd,J=8.5,1.9Hz,2H),7 .43–7.40(m,4H),7.15(dd,J=8.8,0.6Hz,2H),7.07–7.05(m,2H),7.01–6.95(m,4H),6.81(tt,J=7.3,1.3Hz,2H),6.75(s,2H),6.14–6.1 0(m,4H),5.24(d,J=8.7Hz,2H),4.24–4.13(m,2H),3.58–3.49(m,2H),1.66(d,J=14.6Hz,2H),1.57(s,18H),1.51(d,J=14.6Hz,2H),1.2 4(s,18H),1.20(s,6H),1.14(s,6H),0.90(t,J=9.6Hz,2H),0.87–0.81(m,2H),0.72(s,18H),0.61(d,J=11.0Hz,2H),0.27–0.21(m,2H). 13C NMR (126 MHz, benzene-d6) δ 153.50, 151.90, 149.03, 147.62, 143.23, 142.99, 139.92, 139.53, 137.49, 133.42, 129.03, 128.26, 128.17, 127.07, 126.99, 125.40, 125.29, 125.01, 12 2.95,122.79,122.56,120.60,116.40,116.37,116.25,115.82,112.50,109.47,81.81,77.97,56.59,38.25,34.69,34.37,32.18,32.08,31.70,31.66,31.59,30.07,26.00.

[0487] Example 76: Synthesis of intermediates of ligand 16

[0488]

[0489] Before use, dithiophene was azeotropically dried with toluene (4×10 mL). A clear, colorless solution of deoxygenated anhydrous THF (40 mL) in a nitrogen-filled glove box of thiophene (1.974 g, 2.534 mmol, 1.00 equivalent) was placed in a refrigerator cooled to -35°C for 20 hours, and then a pre-cooled n-BuLi solution (3.0 mL, 7.601 mmol, 3.00 equivalent, titrated to 2.50 M / hexane) was added dropwise via a syringe. The now golden brown mixture was placed in the refrigerator for 3 hours, then removed and solid 1,2-dibromotetrachloroethane (2.723 g, 8.361 mmol, 3.30 equivalent) was added dropwise while stirring (500 rpm). After stirring at 23° C. for 2.5 hours, the now golden solution was removed from the glove box, neutralized with brine (50 mL), diluted with CH2Cl2 (20 mL) and water (20 mL), poured into a separatory funnel, separated, and the residual organics were extracted from the aqueous layer using CH2Cl2 (2×20 mL), combined, dried over solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography; hexane to 65% CH2Cl2 in hexane to give dibromothiophene (2.054 g, 2.192 mmol, 87%) as a golden amorphous oil. NMR indicated pure product.

[0490] 1H NMR (400MHz, chloroform-d) δ7.34(d,J=2.5Hz,2H),7.27–7.22(m,2H),7.21(s,2H),6.79(d,J=8.6Hz,2H),4.76(s,4H),3.95-3. 87(m,4H),3.56(q,J=7.1Hz,4H),1.78(q,J=3.0Hz,4H),1.69(s,4H),1.33(s,12H),1.03(t,J=7.1Hz,6H),0.73(s,18H). 13 C NMR (101 MHz, chloroform- d ) δ 153.87, 151.11, 142.13, 132.55, 128.60, 126.64, 122.97, 122.58, 111.68, 98.66, 96.83, 68.02, 65.15, 56.81, 38.00, 32.33, 31.81, 31.62, 25.94, 14.87.

[0491] Example 77: Synthesis of intermediates of ligand 16

[0492]

[0493] A white heterogeneous mixture of iodophenol (3.240 g, 9.304 mmol, 2.00 equiv), K2CO3 (3.858 g, 27.912 mmol, 6.00 equiv) and 1,4-dibromobutane (0.56 mL, 4.652 mmol, 1.00 equiv) in acetone (50 mL) equipped with a reflux condenser was placed in a mantle heated to 60° C. under nitrogen and removed from the mantle after stirring (500 rpm) for 36 hours. The white heterogeneous mixture was removed, cooled to 23°C, diluted with CH2Cl2 (50 mL), stirred for 2 minutes, filtered with suction on a pad of celite, rinsed with CH2Cl2 (4×20 mL), and the resulting light yellow filtrate was concentrated onto celite and purified by silica gel chromatography using an ISCO chromatography purification system; hexane-50% CH2Cl2 in hexane solution to give iodophenyl ether (3.180 g, 4.426 mmol, 95%) as a white solid. NMR indicated pure product.

[0494] 1 H NMR (500 MHz, chloroform-d) δ 7.73 (d, J = 2.4 Hz, 2H), 7.28–7.24 (m, 2H), 6.73 (d, J = 8.6 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). 13CNMR (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.

[0495] Example 78: Synthesis of intermediates of ligand 16

[0496]

[0497] A clear, colorless solution of the starting phenol (3.324 g, 16.110 mmol, 1.00 equiv), KI (3.477 g, 20.943 mmol, 1.30 equiv) and aqueous NaOH (21 mL, 20.943 mmol, 1.30 equiv, 1 N) in methanol (100 mL) and water (50 mL) was placed in an ice bath and stirred vigorously for 1 h under nitrogen, followed by the dropwise addition of pre-chilled commercial aqueous bleach (26 mL, 20.943 mmol, 1.30 equiv, 5.2% w / w) over 10 min. The now opaque, pale yellow mixture was stirred at 0° C. for 2 hours. The mixture was removed from the ice-water bath and stirred at 23° C. for 3 hours. Solid NaH PO (20 g) was added followed by a saturated aqueous Na S O mixture (100 mL) to reduce residual iodine and water (100 mL). The mixture was stirred vigorously for 10 minutes, diluted with CHCl (50 mL), and the biphasic yellow mixture was poured into a separatory funnel and separated. The organics were washed with aqueous Na S O (2×50 mL). The residual organics were extracted from the aqueous layer using CHCl (2×50 mL), combined, dried over solid Na SO, decanted, concentrated onto celite, and purified by silica gel chromatography; hexane-25% CHCl to give o-iodophenol (3.240 g, 9.340 mmol, 58%) as a clear, colorless, amorphous foam. NMR indicated pure product.

[0498] 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.

[0499] Example 79: Synthesis of Ligand 17

[0500]

[0501] Before use, the dibromide was azeotropically dried with toluene (4×10 mL). In a nitrogen-filled glove box, a mixture of the dibromide (0.959 g, 1.241 mmol, 1.00 equiv), carbazole (1.734 g, 6.207 mmol, 5.00 equiv), Cu2O (0.888 g, 6.207 mmol, 5.00 equiv) and K2CO3 (3.431 g, 24.826 mmol, 20.0 equiv) in a dried flask equipped with a stirring bar and a reflux condenser was suspended in anhydrous deoxygenated xylene (30.0 mL), and neat N,N'-dimethylethylenediamine (1.34 mL, 12.413 mmol, 10.00 equiv) was added via syringe, and then the mixture was sealed under nitrogen and mixed. The product was removed from the glove box, placed under nitrogen, and placed in a mantle heated to 140°C with vigorous stirring (1000 rpm) for 72 hours. The dark red heterogeneous mixture was removed from the mantle, allowed to gradually cool to 23°C, diluted with CHCl (30 mL), and vigorously stirred (1000 rpm) for 2 minutes. The mixture was suction filtered over silica gel using CHCl as the eluent, rinsed with CHCl (4 × 25 mL), and the golden-orange filtrate was concentrated onto celite and purified by silica gel chromatography; 25%-100% CHCl in hexanes to give biscarbazolyl-thiophene (0.245 g, 0.2095 mmol, 17%) as a white solid. NMR indicated the product. The product was used in subsequent reactions without further purification.

[0502] To a solution of protected hydroxythiophene (0.245 g, 0.2095 mmol, 1.00 equiv) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL) at 23°C under nitrogen. After vigorous stirring (1000 rpm) for 16 hours, the light golden brown solution was diluted with aqueous HCl (20 mL, 1 N) and CHCl (20 mL), poured into a separatory funnel, and separated. The organics were washed with aqueous HCl (1 x 20 mL). The remaining organics were extracted from the aqueous layer with CHCl (2 x 20 mL). The combined organics were dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography; 10% to 50% CHCl in hexanes to afford hydroxythiophene (0.160 g, 0.1519 mmol, 73%, 12% over two steps) as a light yellow foam. NMR indicated pure product.

[0503] 1H NMR (500MHz, chloroform-d) δ8.17(dd,J=2.0,0.6Hz,4H),7.46(dd,J=8.6,1.9Hz,4H),7.31(d,J=0.6Hz,4H),7.13(dd,J=2.1,1. 3Hz, 2H), 7.12 (s, 2H), 6.89–6.86 (m, 4H), 4.00 (t, J = 3.9Hz, 4H), 3.87 (s, 6H), 1.87 (q, J = 3.4, 2.8Hz, 4H), 1.49 (s, 36H). 13 C NMR (126 MHz, chloroform-d) δ 155.16, 148.33, 147.80, 143.18, 140.45, 130.73, 125.84, 123.68, 123.55, 119.35, 116.42, 116.32, 115.91, 115.78, 114.47, 109.74, 70.89, 55.80 (d, J = 1.9 Hz), 34.78, 32.10, 26.07.

[0504] Characterization of protected ligands:

[0505] 1 H NMR (400MHz, chloroform-d) δ8.06 (dd, J=1.9, 0.6Hz, 4H), 7.42 (dd, J=8.6, 1.9Hz, 4H), 7.32 ( dd,J=8.5,0.6Hz,4H),7.29(s,2H),7.13(d,J=3.1Hz,2H),6.91(d,J=9.0Hz,2H),6. 83(dd,J=8.9,3.1Hz,2H),4.49(s,4H),4.03(q,J=3.5,2.7Hz,4H),3.79(s,6H),2.8 2(q,J=7.0Hz,4H),1.98(q,J=3.3,2.8Hz,4H),1.42(s,36H),0.52(t,J=7.0Hz,6H). 13 C NMR (101 MHz, chloroform-d) δ 153.51, 150.88, 148.81, 143.30, 140.35, 131.83, 125.32, 123.81, 123.41, 120.59, 116.48, 116.02, 113.97, 113.83, 109.98, 96.71, 69.15, 64.48, 55.81, 34.70, 31.97, 26.44, 14.16.

[0506] Example 80: Synthesis of Main Catalyst 37

[0507]

[0508] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (2.41 mL) white heterogeneous mixture of thiophene (14.0 mg, 0.0133 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (6.1 mg, 0.0133 mmol, 1.00 equivalent) C6D6 (0.25 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) directly used in polymerization experiments after filtration.

[0509] 1 H NMR (500MHz, benzene-d6) δ8.46(dd,J=2.0,0.6Hz,2H),8.24(dd,J=1.9,0.6Hz,2H),7.68(dd,J=8.5,0.6Hz,2H),7.50(ddd,J=8.5,5 .5,1.9Hz,4H),7.36(dd,J=8.7,0.6Hz,2H),7.05–7.01(m,2H),6.99–6.96(m,2H),6.80–6.75(m,4H),6.60(s,2H),6.41(dd,J =9.0,3.2Hz,2H),6.22(dd,J=8.3,1.3Hz,4H),5.11(d,J=9.0Hz,2H),4.03(t,J=10.8Hz,2H),3.34(dt,J=11.3,5.9Hz,2H),3. 19(s,6H),1.46(s,18H),1.28(s,18H),1.07(d,J=12.1Hz,2H),0.90–0.78(m,2H),0.68–0.61(m,2H),0.58(d,J=12.1Hz,2H). 13C NMR (126 MHz, benzene-d6) δ 157.29, 151.84, 149.26, 147.05, 143.40, 143.05, 140.02, 139.70, 133.10, 130.56, 129.63, 128.33, 128.03, 127.30, 126.71, 125.2 4,124.90,124.12,122.82,122.74,120.67,116.69,116.41,115.92,115.73,112.46,109.47,74.26,71.94,54.77,34.57,34.43,31.96,31.71,25.80.

[0510] Example 81: Synthesis of Primary Catalyst 38

[0511]

[0512] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.51 mL) white heterogeneous mixture of thiophene (9.0 mg, 0.00854 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added HfBn4 (4.7 mg, 0.00854 mmol, 1.00 equivalent) C6D6 (0.20 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.005 M C6D6 solution. NMR indicates the product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0513] 1H NMR (500MHz, benzene-d6) δ8.48(dd,J=1.9,0.6Hz,2H),8.24(dd,J=2.0,0.6Hz,2H),7.66(dd,J=8.5,0.6Hz,2H),7.51–7.46(m ,4H),7.27(dd,J=8.7,0.6Hz,2H),7.09–7.06(m,4H),6.79(d,J=3.2Hz,2H),6.76(tt,J=7.4,1.3Hz,2H),6.60(s,2H),6 .43(dd,J=9.0,3.2Hz,2H),6.26–6.23(m,4H),5.11(d,J=9.0Hz,2H),4.12–3.99(m,2H),3.45–3.35(m,2H),3.19(s,6H) ,1.46(s,18H),1.28(s,18H),0.92(d,J=13.1Hz,2H),0.81(t,J=9.6Hz,2H),0.60–0.50(m,2H),0.31(d,J=13.2Hz,2H). 13 C NMR (126 MHz, benzene-d6) δ 157.44, 151.88, 149.10, 147.94, 143.45, 143.05, 139.96, 139.68, 132.76, 129.70, 128.01, 126.98, 126.94, 125.34, 124.97, 124.58, 122.66, 120.67, 116.56, 116.40, 116.17, 115.97, 115.68, 112.58, 109.48, 81.98, 78.16, 54.80, 34.58, 34.44, 31.97, 31.72, 25.99.

[0514] Example 82: Synthesis of intermediates of ligand 17

[0515]

[0516] Before use, dithiophene was azeotropically dried with toluene (4×10 mL). A transparent purple-black solution of deoxygenated anhydrous THF (35 mL) of thiophene (1.113 g, 1.810 mmol, 1.00 equivalent) in a nitrogen-filled glove box was placed in a refrigerator cooled to -35°C for 20 hours, and then a pre-cooled n-BuLi solution (2.20 mL, 5.431 mmol, 3.00 equivalent, titrated 2.50 M / hexane) was added dropwise via a syringe. The now golden-purple-brown solution was allowed to stand in the refrigerator for 3 hours, then removed and solid 1,2-dibromotetrachloroethane (1.945 g, 5.974 mmol, 3.30 equivalent) was added dropwise while stirring (500 rpm). After stirring at 23° C. for 2.5 hours, the now clear golden solution was removed from the glove box, neutralized with brine (50 mL), diluted with CH2Cl2 (20 mL) and water (20 mL), poured into a separatory funnel, separated, and the residual organics were extracted from the aqueous layer using CH2Cl2 (2×20 mL), combined, dried over solid Na2SO4, decanted, concentrated onto celite, and purified by silica gel chromatography; 10%-100% CH2Cl2 in hexanes to give dibromothiophene (0.959 g, 1.241 mmol, 69%) as a golden amorphous oil. NMR indicated pure product.

[0517] 1 H NMR (400MHz, chloroform-d) δ7.23 (s, 2H), 6.95 (dd, J = 2.7, 0.8Hz, 2H), 6.83–6.80 (m, 4H), 4.82 (s, 4H), 3. 84(p,J=3.2Hz,4H),3.75(s,6H),3.50(q,J=7.1Hz,4H),1.78–1.67(m,4H),1.00(t,J=7.0Hz,6H). 13 C NMR (101 MHz, chloroform- d ) δ 153.46, 151.13, 150.55, 132.14, 124.62, 123.13, 116.00, 114.24, 98.86, 97.08, 69.03, 65.15, 55.76, 25.95, 14.79.

[0518] Example 83: Synthesis of intermediates of ligand 17

[0519]

[0520] A mixture of thiophene (2.363 g, 8.315 mmol, 3.00 equiv, 67% purity), K3PO4 (5.884 g, 27.720 mmol, 9.00 equiv), Pd(AmPhos)Cl2 (0.436 g, 0.6160 mmol, 0.20 equiv), and bisphenyliodonium (1.707 g, 3.080 mmol, 1.00 equiv) was prepared. The mixture was evacuated and then backfilled with nitrogen three more times, followed by the sequential addition of deoxygenated 1,4-dioxane (40.0 mL) and deoxygenated water (4.0 mL) via syringe. The mixture was then placed in a hood heated to 50°C. After stirring (1000 rpm) for 36 hours, the black mixture was removed from the hood, gradually cooled to 23 ° C, filtered with suction on a silica gel pad, washed with CH2Cl2 (4×20 mL), and the clear black filtrate was concentrated. Residual 1,4-dioxane was removed by rotary evaporation with toluene (2×10 mL). The black mixture was then suspended in CH2Cl2 (20 mL), filtered with suction on a silica gel pad, rinsed with CH2Cl2 (4×20 mL), and the black filtrate was concentrated onto celite and purified by silica gel chromatography using an ISCO chromatography purification system; 25%-100% CH2Cl2 in hexane to give bithiophene (1.113 g, 1.810 mmol, 59%) as a dark purple-black viscous oil. NMR indicated pure product.

[0521] 1 H NMR (400MHz, chloroform-d) δ7.27(d,J=3.4Hz,2H),7.01(d,J=2.9Hz,2H),6.83(d,J=8.9Hz,2H),6.78(dd,J=8.9,3.0Hz,2H),6.64(d,J =3.5Hz,2H),5.10(s,4H),3.86–3.78(m,4H),3.77(s,6H),3.66(q,J=7.1Hz,4H),1.70(h,J=2.7Hz,4H),1.18(t,J=7.1Hz,6H). 13 C NMR (101 MHz, chloroform- d ) δ 153.31, 153.23, 150.66, 129.60, 125.10, 123.38, 116.70, 114.26, 113.27, 100.85, 94.87, 69.11, 64.13, 55.67, 26.07, 15.08.

[0522] Example 84: Synthesis of intermediates of ligand 17

[0523]

[0524] A white heterogeneous mixture of 2-iodophenol (1.890 g, 7.559 mmol, 2.00 equiv), KCO (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. under nitrogen and removed from the mantle after stirring (500 rpm) for 36 hours. The white heterogeneous mixture was removed, cooled to 23°C, diluted with CH2Cl2 (50 mL), stirred for 2 minutes, filtered with suction on a pad of celite, rinsed with CH2Cl2 (4×20 mL), and the resulting light yellow filtrate was concentrated onto celite and purified by silica gel chromatography using an ISCO chromatography purification system; 50%-100% CH2Cl2 in hexane to give iodophenyl ether (1.945 g, 3.510 mmol, 93%) as a white solid. NMR indicated pure product.

[0525] 1 H NMR (500MHz, chloroform-d) δ7.32 (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 C NMR (126 MHz, chloroform-d) δ 154.26, 152.05, 124.61, 114.78, 113.06, 86.94, 69.58, 55.92, 26.15.

[0526] Example 85: Synthesis of intermediates of ligand 17

[0527]

[0528] A clear, colorless solution of the starting phenol (5.000 g, 40.277 mmol, 1.00 equiv), KI (7.020 g, 42.291 mmol, 1.05 equiv) and aqueous NaOH (201 mL, 201.39 mmol, 5.00 equiv, 1 N) in methanol (300 mL) and water (200 mL) was placed in an ice bath under nitrogen and stirred vigorously for 1 h, followed by the addition of pre-chilled commercial aqueous bleach (61 mL, 42.291 mmol, 1.05 equiv, 5.2% w / w) dropwise over 30 min. The now dark orange mixture was stirred at 0° C. for 30 minutes, removed from the ice-water bath, solid NaH PO (30 g) was added followed by aqueous Na S O (200 mL) to reduce residual iodine and water (200 mL), the mixture was stirred vigorously for 10 minutes, diluted with CHCl (50 mL), the biphasic dark reddish orange mixture was poured into a separatory funnel, separated, the organics washed with aqueous Na S O (2×50 mL), the residual organics were extracted from the aqueous layer using CHCl (2×50 mL), combined, dried over solid Na SO, decanted, concentrated onto celite, and purified by silica gel chromatography; 25% CHCl in hexanes to 100% CHCl to give o-iodophenol (0.877 g, 3.508 mmol, 9%) as a light purple amorphous foam and recovered starting phenol (1.277 g, 10.287 mmol, 26%). NMR indicated pure product.

[0529] 1 H 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 C NMR (126 MHz, chloroform-d) δ 153.93, 149.17, 122.66, 116.37, 115.13, 85.07, 55.99.

[0530] Example 86: Synthesis of Ligand 18

[0531]

[0532] Before use, the dibromide was azeotropically dried with toluene (4×10 mL). In a nitrogen-filled glove box, a mixture of the dibromide (1.368 g, 1.828 mmol, 1.00 equiv), carbazole (2.553 g, 9.138 mmol, 5.00 equiv), Cu2O (1.308 g, 9.140 mmol, 5.00 equiv) and K2CO3 (5.053 g, 36.560 mmol, 20.0 equiv) in a dried flask equipped with a stirring bar and a reflux condenser was suspended in anhydrous deoxygenated xylene (40.0 mL), and neat N,N'-dimethylethylenediamine (2.00 mL, 18.280 mmol, 10.00 equiv) was added via syringe, and then the mixture was sealed under nitrogen and mixed. The product was removed from the glove box, placed under nitrogen, and placed in a mantle heated to 140° C. with vigorous stirring (1000 rpm) for 72 hours. The dark red heterogeneous mixture was removed from the mantle, allowed to gradually cool to 23° C., diluted with CHCl (30 mL), and vigorously stirred (1000 rpm) for 2 minutes. The mixture was suction filtered onto silica gel using CHCl as the eluent, rinsed with CHCl (4×25 mL), and the golden orange filtrate was concentrated onto celite and purified by silica gel chromatography; 25%-60% CHCl in hexanes to give biscarbazolyl-thiophene (0.116 g, 0.1013 mmol, 6%) as a light golden foam. NMR indicated the product.

[0533] To a solution of protected hydroxythiophene (0.116 g, 0.1013 mmol, 1.00 equiv) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL) at 23°C under nitrogen. After vigorous stirring (1000 rpm) for 16 hours, the light golden brown solution was diluted with aqueous HCl (20 mL, 1 N) and CHCl (20 mL), poured into a separatory funnel, and separated. The organics were washed with aqueous HCl (1 x 20 mL). The remaining organics were extracted from the aqueous layer with CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography; 10% to 50% CHCl in hexanes to afford hydroxythiophene (70.0 mg, 0.0680 mmol, 73%, 4% over two steps) as a light yellow foam. NMR indicated pure product.

[0534] 1H NMR (500MHz, chloroform-d) δ8.10(d,J=1.9Hz,4H),7.39(dd,J=8.5,1.9Hz,4H),7.28–7.24(m,2H),7.21(d,J=8.4Hz,6H),6.98(d dd,J=9.0,7.6,3.2Hz,2H),6.83(dd,J=9.0,4.5Hz,2H),6.63(s,2H),4.01–3.94(m,4H),1.88–1.82(m,4H),1.43(s,36H). 19 F NMR (470 MHz, chloroform-d) δ -121.03 (td, J = 8.3, 4.6 Hz).

[0535] Example 87: Synthesis of Primary Catalyst 39

[0536]

[0537] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.49 mL) white heterogeneous mixture of thiophene (8.5 mg, 0.00826 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (3.8 mg, 0.00826 mmol, 1.00 equivalent) C6D6 (0.16 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) directly used in polymerization experiments after filtration.

[0538] 1H NMR (400MHz, benzene-d6) δ8.37(d,J=1.8Hz,2H),8.27–8.24(m,2H),7.56(d,J=8.5Hz,2H),7.46(ddd,J=24.0, 8.6,1.9Hz,4H),7.39–7.33(m,2H),6.99–6.94(m,4H),6.80–6.71(m,4H),6.50–6.44(m,2H),6.44(s,2H) ,6.17–6.11(m,4H),5.06(dd,J=9.0,4.8Hz,2H),3.96(t,J=10.3Hz,2H),3.28–3.18(m,2H),1.39(s,18H) ,1.28(s,18H),0.93(d,J=12.0Hz,2H),0.73(t,J=9.1Hz,2H),0.68–0.57(m,2H),0.51(d,J=12.0Hz,2H). 19 FNMR (376 MHz, benzene-d6) δ-116.15 (td, J=8.3, 5.0 Hz). 13 C NMR (101MHz, benzene-d6) δ158.52, 151.78, 151.46 (d, J = 2.7Hz), 143.49 (d, J = 33.9Hz), 139.83 ( d,J=29.4Hz),138.24(d,J=157.9Hz),131.79(d,J=1.3Hz),130.53,130.26,130.17,128. 13,126.91,125.15,124.82,124.55,124.09,122.86,122.82,121.23,117.50,117.17,116.49,115.98,115.83,112.15,109.23,80.63,71.99,34.50,34.43,31.88,31.68,25.53.

[0539] Example 88: Synthesis of Primary Catalyst 40

[0540]

[0541] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.49 mL) white heterogeneous mixture of thiophene (8.4 mg, 0.00816 mmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added HfBn4 (4.4 mg, 0.00816 mmol, 1.00 equivalent) C6D6 (0.16 mL) solution. After stirring (500 rpm) for 1 hour, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.005 M C6D6 solution. NMR indicated the product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0542] 1 H NMR (400MHz, benzene-d6) δ8.39(d,J=1.8Hz,2H),8.28–8.24(m,2H),7.54(d,J=8.4Hz,2H),7.45(ddd,J=21.1,8.6,1.9Hz,4H),7. 31–7.25(m,2H),7.08–6.94(m,1H),6.89(t,J=7.4Hz,1H),6.78(dd,J=8.8,3.2Hz,2H),6.73(tt,J=7.4,1.2Hz,2H),6.51–6 .44(m,4H),6.43(s,2H),6.24–6.18(m,4H),5.03(dd,J=9.0,4.8Hz,2H),3.94(t,J=10.7Hz,2H),3.23(dd,J=14.0,9.5Hz,2 H), 1.39 (s, 18H), 1.28 (s, 18H), 0.90 (d, J = 13.3Hz, 2H), 0.75–0.62 (m, 2H), 0.52 (d, J = 13.1Hz, 2H), 0.24 (d, J = 13.2Hz, 2H). 19 F NMR (376 MHz, benzene-d6) δ -114.85–-116.52 (m). 13C NMR (101 MHz, benzene-d6) δ 159.91 (d, J = 246.6 Hz), 151.69, 151.24 (d, J = 2.8 Hz), 147.23, 143.54 (d, J = 37.1 Hz), 139.73 (d, J = 24.0 Hz), 131.42 (d, J = 1.2 Hz), 130.36, 130.28, 128.54, 12 7.08,126.85,125.29,124.91,122.75,122.71,121.08,117.43,117.31,117.20,116.47 (d,J=5.7Hz),115.70,112.37,109.24,81.73,78.64,34.50,34.44,31.88,31.69,25.76.

[0543] Example 89: Synthesis of Ligand 19

[0544]

[0545] A mixture of thiopheneboropinacol (2.017 g, 2.586 mmol, 3.00 equiv, 72% NMR purity), K3PO4 (1.647 g, 7.758 mmol, 9.00 equiv), Pd(AmPhos)Cl2 (122.0 mg, 0.1724 mmol, 0.20 equiv), and bisphenyliodonium (0.426 g, 0.8620 mmol, 1.00 equiv) was prepared. The mixture was evacuated and then backfilled with nitrogen three more times, followed by the addition of deoxygenated 1,4-dioxane (17.0 mL) and deoxygenated water (1.7 mL) via syringe. The mixture was then placed in a hood heated to 50°C. After vigorous stirring (1000 rpm) for 40 hours, the black mixture was removed from the hood, allowed to gradually cool to 23°C, filtered with suction on a silica gel pad, washed with CHCl (4×20 mL), and the clear black filtrate was concentrated. Residual 1,4-dioxane was removed by rotary evaporation using toluene (2×10 mL). The black mixture was then suspended in CHCl (20 mL), filtered with suction on a silica gel pad, rinsed with CHCl (4×20 mL), and the black filtrate was concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatography purification system; 10%-50% CHCl in hexane to give bithiophene (0.837 g, 0.7544 mmol, 88%) as a red amorphous oil. NMR indicated pure product.

[0546] To a solution of impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) was added concentrated HCl (5 mL) at 23°C under nitrogen. The golden brown solution was stirred (500 rpm) for 20 hours, diluted with 1N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics washed with 1N HCl (1 x 10 mL). The remaining organics were extracted from the aqueous solution with CHCl (2 x 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatography purification system; 10%-75% CHCl in hexane to afford the bithiophene (0.563 g, 0.5668 mmol, 75%, 66% over two steps) as a camel-colored solid. NMR indicated pure product.

[0547] 1 H NMR (500MHz, chloroform-d) δ8.11(d,J=2.0Hz,4H),7.61(dd,J=7.7,1.7Hz,2H),7.40(dd,J=8.6,1.9Hz,4H),7.32(s,2H),7 .30–7.20(m,6H),7.12(t,J=7.5Hz,2H),6.90(d,J=8.2Hz,2H),4.11–4.04(m,4H),1.95–1.87(m,4H),1.43(s,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.

[0548] Characterization of the protected coupling products:

[0549] 1H NMR (500MHz, chloroform-d) δ8.13 (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=3.0Hz,4H),4.30–4.19(m,4H),2.79(qt,J=7.2,2. 7Hz, 4H), 2.29–2.20 (m, 4H), 1.48 (s, 36H), 0.52 (tt, J = 7.1, 2.9Hz, 6H). 13 C NMR (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.

[0550] Example 90: Synthesis of Main Catalyst 41

[0551]

[0552] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.34 mL) transparent colorless solution of thiophene (7.4 mg, 7.45 μmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (3.8 mg, 8.20 μmol, 1.10 equivalent) C6D6 (0.15 mL) solution. After stirring (500 rpm) for 30 minutes, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.0025 M or 0.005 M) directly for polymerization experiments after filtration.

[0553] 1H NMR(500MHz, benzene-d6)δ8.48(dd,J=2.0,0.6Hz,2H),8.22(dd,J=1.9,0.7Hz,2H),7.50–7.46(m,4 H),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. 2Hz,2H),6.23–6.17(m,4H),5.12(dd,J=8.2,1.2Hz,2H),3.97–3.88(m,2H),3.28–3.21(m,2H ),1.49(s,18H),1.28(s,18H),1.06(d,J=12.4Hz,2H),0.77–0.67(m,2H),0.52–0.44(m,4H). 13 C NMR (126 MHz, benzene-d6) δ 156.11, 152.23, 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.

[0554] Example 91: Synthesis of Primary Catalyst 42

[0555]

[0556] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, a transparent, colorless solution of anhydrous C6D6 (2.49 mL) of thiophene (14.0 mg, 14.09 μmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.33 mL) solution of HfBn4 (8.4 mg, 15.50 μmol, 1.10 equivalent). After stirring (500 rpm) for 30 minutes, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.0025 M C6D6 solution. NMR indicated the product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.0025 M) that is directly used in polymerization experiments after filtration.

[0557] 1H NMR (500MHz, benzene-d6) δ8.49(dd,J=2.0,0.6Hz,2H),8.23(dd,J=2.0,0.6Hz,2H),7.47(ddd,J=8.8,5.0,1.9Hz,4H),7.27(d dd,J=8.5,4.4,1.2Hz,4H),7.17(dd,J=8.7,0.6Hz,2H),6.99–6.95(m,4H),6.86(s,2H),6.78(dddd,J=8.6,7.3,3.6,1. 5Hz,4H),6.71(td,J=7.6,1.2Hz,2H),6.22–6.16(m,4H),5.15(dd,J=8.2,1.2Hz,2H),4.02–3.93(m,2H),3.35–3.26(m, 2H), 1.50 (s, 18H), 1.28 (s, 18H), 0.89 (d, J = 13.3Hz, 2H), 0.78–0.68 (m, 2H), 0.47–0.36 (m, 2H), 0.22 (d, J = 13.3Hz, 2H). 13 C 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.

[0558] Example 92: Synthesis of intermediates of ligand 19

[0559]

[0560] In a nitrogen-filled, continuously purged glove box, a mixture of bromothiophene (5.883 g, 24.811 mmol, 1.00 equivalent), 3,6-di-tert-butylcarbazole (15.252 g, 54.585 mmol, 2.20 equivalent), Cu2O (7.100 g, 49.622 mmol, 2.00 equivalent) and K2CO3 (34.290 g, 248.11 mmol, 10.00 equivalent) was suspended in deoxygenated anhydrous xylene (200 mL), N,N'-DMEDA (21.5 mL, 199.84 mmol, 4.00 equivalent) was added, and the mixture was equipped with a reflux condenser and a rubber septum. The mixture was removed from the glove box, placed under nitrogen, placed in a mantle heated to 140° C., stirred vigorously (1000 rpm) for 72 hours, removed from the mantle, and the now dark red-black mixture was gradually cooled to 23° C. CHCl (100 mL) was added, and the mixture was stirred for 5 minutes. The mixture was suction filtered onto a silica gel pad, rinsed with CHCl (4×75 mL), and the golden brown filtrate was concentrated onto celite and purified several times by silica gel chromatography using an ISCO chromatography purification system; 15% CHCl in hexanes gave the thiophene-carbazole product (7.699 g, 17.673 mmol, 71%) as a white amorphous foam. NMR indicated pure product.

[0561] 1 H NMR (500MHz, chloroform-d) δ8.12(d,J=1.9Hz,2H),7.45(dd,J=8.6,2.0Hz,2H),7.32(d,J=3.6Hz,1H),7.20 (d, J=8.6Hz, 2H), 6.89 (d, J=3.6Hz, 1H), 3.56 (q, J=7.1Hz, 2H), 1.47 (s, 18H), 1.16 (t, J=7.1Hz, 3H). 13 C NMR (126 MHz, chloroform- d ) δ 150.87, 142.60, 139.70, 127.62, 123.44, 123.08, 120.21, 116.07, 109.57, 102.36, 94.78, 64.37, 34.70, 32.03, 15.01.

[0562] Example 93: Synthesis of intermediates of ligand 19

[0563]

[0564] A golden yellow solution of thiophene (3.000 g, 6.887 mmol, 1.00 equiv) in anhydrous deoxygenated Et2O (75 mL) in a nitrogen-filled glove box was placed in a refrigerator (-35° C.) and pre-cooled for 14 hours before adding pre-cooled n-BuLi solution (3.50 mL, 8.608 mmol, 1.25 equiv, titrated to 2.5 M / hexane) in a rapid dropwise manner. The light orange solution was allowed to stand in the refrigerator for 4 hours before adding neat isopropanol boropinacol ester (2.81 mL, 13.774 mmol, 2.00 equiv). The now golden solution was stirred at 23° C. for 2 hours. The now white heterogeneous mixture was diluted with aqueous phosphate buffer (20 mL, pH=8, 0.05 M) and concentrated by rotary evaporation. The mixture was diluted with CH2Cl2 (25 mL) and water (25 mL), poured into a separatory funnel, separated, and the organics were washed with water (1×25 mL). The remaining organics were extracted with CH2Cl2 (2×25 mL), combined, dried over solid Na2SO4, decanted, and concentrated. The resulting golden foam was dissolved in CH2Cl2 (10 mL), filtered through a short pad of silica gel, rinsed with CH2Cl2 (4×20 mL), and the golden filtrate solution was concentrated to give thiophene-boropinacol ester (2.581 g, 4.596 mmol, 67% to 72% NMR purity) as a light golden foam. The impure product was used in subsequent reactions without further purification.

[0565] 1 H NMR (500MHz, chloroform-d) δ8.11–8.08(m,2H),7.62(d,J=0.9Hz,1H),7.45(dt,J=8.6,1.4Hz,2H),7.23(dd,J=8.7 ,0.7Hz,2H),4.88(d,J=0.8Hz,2H),2.96–2.88(m,2H),1.46(s,18H),1.38(s,12H),0.58(t,J=7.1Hz,3H). 13 C NMR (126 MHz, chloroform- d ) δ 158.93, 142.70, 139.53, 130.88, 127.58, 123.65, 123.00, 115.86, 109.77, 98.24, 84.20, 64.53, 34.71, 32.03, 24.80, 14.14.

[0566] Example 94: Synthesis of Ligand 20

[0567]

[0568] A mixture of thiopheneboropinacol (0.605 g, 0.5387 mmol, 2.70 equiv, 50% NMR purity), K3PO4 (0.343 g, 1.616 mmol, 8.10 equiv), Pd(AmPhos)Cl2 (28.3 mg, 0.0399 mmol, 0.20 equiv), and bisphenyliodonium (0.143 g, 0.2000 mmol, 1.00 equiv) was prepared. The mixture was evacuated and then backfilled with nitrogen three more times, followed by the addition of deoxygenated 1,4-dioxane (4.0 mL) and deoxygenated water (0.4 mL) via syringe. The mixture was then placed in a hood heated to 50°C. After vigorous stirring (1000 rpm) for 40 hours, the black mixture was removed from the hood, allowed to gradually cool to 23 ° C, filtered with suction on a silica gel pad, washed with CHCl (4 × 20 mL), and the clear black filtrate was concentrated. Residual 1,4-dioxane was removed by rotary evaporation with toluene (2 × 10 mL). The black mixture was then suspended in CHCl (20 mL), filtered with suction on a silica gel pad, rinsed with CHCl (4 × 20 mL), and the black filtrate was concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatography purification system; 10%-50% CHCl in hexane to give bithiophene (0.168 g) as an off-white solid. NMR indicated the product contained a small amount of impurities. The material was used for subsequent deprotection without further purification.

[0569] To the impure coupled product in CHCl-1,4-dioxane (8 mL, 1:1) was added concentrated HCl (4 mL) at 23°C under nitrogen. The golden brown solution was stirred (500 rpm) for 20 hours, diluted with 1N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics washed with 1N HCl (1 x 10 mL). The remaining organics were extracted from the aqueous solution with CHCl (2 x 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatography purification system; 10%-50% CHCl in hexane to afford the bithiophene (80.0 mg, 0.0657 mmol, 33% two steps) as a camel-colored solid. NMR indicated pure product.

[0570] 1H NMR (400MHz, chloroform-d) δ8.11(d,J=1.9Hz,4H),7.57(d,J=2.3Hz,2H),7.47(s,2H),7.41(dd,J=8.7,1.9Hz,4H),7.31(s,2H),7.27–7 .20(m,4H),6.78(d,J=8.6Hz,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.

[0571] Example 95: Synthesis of Primary Catalyst 43

[0572]

[0573] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.09 mL) transparent colorless solution of thiophene (7.4 mg, 6.08 μmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (3.0 mg, 6.69 μmol, 1.10 equivalent) C6D6 (0.13 mL) solution. After stirring (500 rpm) for 30 minutes, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) directly used for polymerization experiments after filtration.

[0574] 1H NMR (400MHz, benzene-d6) δ8.55(d,J=1.9Hz,2H),8.15–8.11(m,2H),7.57(d,J=2.5Hz,2H),7.51(dd,J=8.6,1.9Hz,2H),7.43(dd,J=8.7,1.9Hz,2H),7 .34(d,J=8.4Hz,2H),7.21(dd,J=8.7,0.6Hz,2H),7.09–7.04(m,2H),7. 03–6.97(m,2H),6.98–6.94(m,2H),6.84(s,2H),6.86–6.81(m,2H),6.24 –6.17(m,4H),5.17(d,J=8.7Hz,2H),4.08–3.98(m,2H),3.42–3.34(m,2 H),1.68(d,J=14.6Hz,2H),1.57(s,18H),1.51(d,J=14.6Hz,2H),1.23(s ,18H),1.20(s,6H),1.16(s,6H),1.02(d,J=12.3Hz,2H),0.89(q,J=11. 9,10.7Hz,2H),0.70(s,18H),0.64–0.56(m,2H),0.52(d,J=12.3Hz,2H). 13 C 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.

[0575] Example 96: Synthesis of Primary Catalyst 44

[0576]

[0577] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, a transparent, colorless solution of anhydrous C6D6 (1.19 mL) of thiophene (8.3 mg, 6.82 μmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.17 mL) solution of HfBn4 (4.1 mg, 7.50 μmol, 1.10 equivalent). After stirring (500 rpm) for 30 minutes, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.005 M C6D6 solution. NMR indicated the product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0578] 1 H NMR (500MHz, benzene-d6) δ8.57(dd,J=1.9,0.6Hz,2H),8.15(dd,J=2.0,0.7Hz,2H),7.58(d,J=2.5Hz,2H),7.52(dd,J=8.5,1.9Hz,2H),7.42(dd ,J=8.7,1.9Hz,2H),7.33(dd,J=8.5,0.6Hz,2H),7.14–7.07(m,6H),7.05–7.02(m,2H),6.85(s,2H),6.82(tt,J=7.3,1.2Hz,2H),6.24–6.1 8(m,4H),5.21(d,J=8.7Hz,2H),4.15–4.06(m,2H),3.50–3.41(m,2H),1.69(d,J=14.6Hz,2H),1.59(s,18H),1.53(d,J=14.7Hz,2H),1.25( s,18H),1.22(s,6H),1.17(s,6H),0.92(t,J=9.5Hz,2H),0.84(d,J=13.2Hz,2H),0.72(s,18H),0.59–0.51(m,2H),0.27(d,J=13.2Hz,2H). 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.

[0579] Example 97: Synthesis of Ligand 21

[0580]

[0581] A mixture of thiopheneboropinacol (2.017 g, 2.586 mmol, 3.00 equiv, 72% NMR purity), K3PO4 (1.647 g, 7.758 mmol, 9.00 equiv), Pd(AmPhos)Cl2 (122.0 mg, 0.1724 mmol, 0.20 equiv), and bisphenyliodonium (0.478 g, 0.8620 mmol, 1.00 equiv) was prepared. The mixture was evacuated and then backfilled with nitrogen three more times, followed by the addition of deoxygenated 1,4-dioxane (17.0 mL) and deoxygenated water (1.7 mL) via syringe. The mixture was then placed in a hood heated to 50°C. After vigorous stirring (1000 rpm) for 40 hours, the black mixture was removed from the hood, allowed to gradually cool to 23°C, filtered with suction on a silica gel pad, washed with CHCl (4×20 mL), and the clear black filtrate was concentrated. Residual 1,4-dioxane was removed by rotary evaporation using toluene (2×10 mL). The black mixture was then suspended in CHCl (20 mL) and filtered with suction on a silica gel pad, rinsed with CHCl (4×20 mL). The black filtrate was then concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatography purification system; 10%-50% CHCl in hexane to give bithiophene (0.747 g, 0.6387 mmol, 74%) as a red amorphous oil. NMR indicated pure product.

[0582] To a solution of the impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) was added concentrated HCl (5 mL) at 23°C under nitrogen. The golden brown solution was stirred (500 rpm) for 20 hours, diluted with 1N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics washed with 1N HCl (1 x 10 mL). The remaining organics were extracted from the aqueous solution with CHCl (2 x 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatography purification system; 10%-75% CHCl in hexanes to afford the bithiophene (0.514 g, 0.4879 mmol, 76%, 57% over two steps) as a camel-colored solid. NMR indicated pure product.

[0583] 1 H NMR (500MHz, chloroform-d) δ8.14(d,J=1.9Hz,4H),7.68(s,2H),7.42(dd,J=8.6,1.9Hz,4H),7.35(s,2H),7.25(d,J=8.6Hz,4H),7.14(d,J=2.9H z, 2H), 6.84 (d, J = 9.0Hz, 2H), 6.79 (dd, J = 8.9, 2.9Hz, 2H), 3.99 (q, J = 3.5, 2.1Hz, 4H), 3.84 (s, 6H), 1.83 (q, J = 2.8Hz, 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.

[0584] Characterization of the protected coupling products:

[0585] 1H NMR (500MHz, chloroform-d) δ8.10(d,J=1.9Hz,4H),7.55(d,J=3.1Hz,2H),7.44(dd,J=8.6,1.9Hz,4H),7.35–7.31(m,6H),6.94(d,J=9.0Hz,2H),6.84(dd, J=9.0,3.1Hz,2H),4.47(s,4H),4.16(d,J=5.0Hz,4H),3.81(s,6H),2.80 (q,J=7.1Hz,4H),2.22–2.12(m,4H),1.46(s,36H),0.52(t,J=7.0Hz,6H). 13 C NMR (126 MHz, chloroform-d) δ 153.53, 150.14, 147.42, 142.73, 139.47, 129.40, 123.90, 123.65, 123.06, 122.44, 119.40, 116.10, 115.94, 114.29, 113.64, 109.85, 96.97, 69.27, 64.70, 55.89, 34.71, 32.04, 26.46, 14.16.

[0586] Example 98: Synthesis of Primary Catalyst 45

[0587]

[0588] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.25 mL) transparent colorless solution of thiophene (7.4 mg, 7.02 μmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (3.7 mg, 7.72 μmol, 1.10 equivalent) C6D6 (0.16 mL) solution. After stirring (500 rpm) for 30 minutes, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare the primary catalyst solution (0.0025 M or 0.005 M) directly used for polymerization experiments after filtration.

[0589] 1H NMR (400MHz, benzene-d6) δ8.47(dd,J=2.0,0.6Hz,2H),8.24(dd,J=1.9,0.6Hz,2H),7.49(td,J=8.6,1.9Hz,4H),7.30(ddd,J=8.5 ,5.3,0.6Hz,4H),7.08–7.03(m,2H),6.96(dtd,J=6.9,1.4,0.7Hz,2H),6.92(d,J=3.1Hz,2H),6.84(s,2H),6.78(tt,J=7.3, 1.3Hz,2H),6.45(dd,J=9.1,3.1Hz,2H),6.31–6.26(m,4H),5.04(d,J=9.1Hz,2H),3.95–3.85(m,2H),3.28–3.19(m,2H),3.1 6(s,6H),1.47(s,18H),1.27(s,18H),1.08(d,J=12.3Hz,2H),0.88–0.74(m,2H),0.58(d,J=12.3Hz,2H),0.56–0.51(m,2H). 13 C NMR (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.

[0590] Example 99: Synthesis of Primary Catalyst 46

[0591]

[0592] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, a transparent colorless solution of anhydrous C6D6 (1.70 mL) of thiophene (10.2 mg, 9.68 μmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.24 mL) solution of HfBn4 (5.8 mg, 10.65 μmol, 1.10 equivalent). After stirring (500 rpm) for 30 minutes, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.005 M C6D6 solution. NMR indicated the product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0593] 1 H NMR (500MHz, benzene-d6) δ8.50(dd,J=2.0,0.6Hz,2H),8.26(dd,J=1.9,0.6Hz,2H),7.50(dd,J=2.5,1.9Hz,2H),7.48(t,J=2. 1Hz,2H),7.29(dd,J=8.5,0.6Hz,2H),7.23(dd,J=8.7,0.6Hz,2H),6.99–6.95(m,2H),6.93(d,J=3.1Hz,2H),6.85(s,2H) ,6.79–6.74(m,2H),6.52–6.44(m,4H),6.32–6.28(m,4H),5.09(d,J=9.0Hz,2H),4.02–3.92(m,2H),3.33–3.25(m,2H),3 .17(s,6H),1.48(s,18H),1.29(s,18H),0.92(d,J=13.3Hz,2H),0.85–0.77(m,2H),0.55(m,2H),0.31(d,J=13.3Hz,2H). 13 C 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.

[0594] Example 100: Synthesis of Ligand 22

[0595]

[0596] A mixture of thiopheneboropinacol (0.605 g, 0.5387 mmol, 2.70 equiv, 50% NMR purity), K3PO4 (0.343 g, 1.616 mmol, 8.10 equiv), Pd(AmPhos)Cl2 (28.3 mg, 0.0399 mmol, 0.20 equiv), and bisphenyliodonium (0.106 g, 0.1995 mmol, 1.00 equiv) was prepared. The mixture was evacuated and then backfilled with nitrogen three more times, followed by the sequential addition of deoxygenated 1,4-dioxane (4.0 mL) and deoxygenated water (0.4 mL) via syringe. The mixture was then placed in a hood heated to 50°C. After vigorous stirring (1000 rpm) for 40 hours, the black mixture was removed from the hood, allowed to gradually cool to 23 ° C, filtered with suction on a silica gel pad, washed with CHCl (4 × 20 mL), and the clear black filtrate was concentrated. Residual 1,4-dioxane was removed by rotary evaporation with toluene (2 × 10 mL). The black mixture was then suspended in CHCl (20 mL) and filtered with suction on a silica gel pad, rinsed with CHCl (4 × 20 mL). The black filtrate was then concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatography purification system; 10%-50% CHCl in hexane to give bithiophene (0.101 g) as an off-white solid. NMR indicated the product contained a small amount of impurities. The material was used for subsequent deprotection without further purification.

[0597] To a solution of the impure coupled product in CHCl-1,4-dioxane (6 mL, 1:1) was added concentrated HCl (3 mL) at 23°C under nitrogen. The golden brown solution was stirred (500 rpm) for 20 hours, diluted with 1N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics washed with 1N HCl (1 x 10 mL). The remaining organics were extracted from the aqueous solution with CHCl (2 x 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatography purification system; 10%-75% CHCl in hexanes to afford the bithiophene (52.0 mg, 0.05052 mmol, 25% two steps) as a camel-colored solid. NMR indicated pure product.

[0598] 1H NMR (400MHz, chloroform-d) δ8.10(d,J=1.9Hz,4H),7.43–7.29(m,8H),7.25(d,J=10.3Hz,2H),7.19(d,J=8.6Hz,4H),6.90 (td,J=8.2,7.5,3.0Hz,2H),6.80(dd,J=9.1,4.6Hz,2H),4.01(d,J=4.8Hz,4H),1.92–1.81(m,4H),1.42(s,36H). 19 F NMR (376 MHz, chloroform-d) δ-120.34 (td, J=8.5, 4.7 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.

[0599] Characterization of the protected coupled thiophene: 1H NMR (400 MHz, chloroform-d) δ 8.08 (dd, J = 1.9, 0.7 Hz, 4H), 7.78 (dd, J = 9.7, 2.9 Hz, 2H), 7.42 (dd, J = 8.6, 1.9 Hz, 4H), 7.33 (s, 2H), 7.31–7.26 (m, 4H), 7.02–6.86 (m, 4H), 4.43 (s, 4H), 4.20–4.14 (m, 4H), 2.86 (q, J = 7.0 Hz, 4H), 2.25–2.15 (m, 4H), 1.43 (s, 38H), 0.55 (t, J = 7.1 Hz, 6H). 19F NMR (376 MHz, chloroform-d) δ-123.44 (ddd, J=9.9, 7.4, 4.8 Hz).

[0600] Example 101: Synthesis of Primary Catalyst 47

[0601]

[0602] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.61 mL) transparent colorless solution of thiophene (9.2 mg, 8.94 μmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (4.5 mg, 9.83 μmol, 1.10 equivalent) C6D6 (0.18 mL) solution. After stirring (500 rpm) for 30 minutes, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) directly used for polymerization experiments after filtration.

[0603] 1 H NMR (500MHz, benzene-d6) δ8.42(dd,J=2.0,0.6Hz,2H),8.28(dd,J=1.9,0.7Hz,2H),7.51(dd,J=8.7,1.9Hz,2H),7.44(dd,J=8.5,1.9 Hz,2H),7.33(dd,J=8.7,0.6Hz,2H),7.21(dd,J=8.5,0.7Hz,2H),7.01–6.95(m,2H),6.83(s,2H),6.79–6.74(m,2H),6.50(ddd, J=9.0,7.4,3.2Hz,4H),6.36–6.32(m,2H),6.27–6.23(m,4H),4.99(dd,J=9.0,4.8Hz,2H),3.87–3.75(m,2H),3.11(dd,J=11.8 ,4.6Hz,2H),1.43(s,18H),1.30(s,18H),1.02(d,J=12.4Hz,2H),0.98–0.82(m,2H),0.75–0.63(m,2H),0.52(d,J=12.3Hz,2H). 19 FNMR (470 MHz, benzene-d6) δ -114.74–-117.39 (m). 13C 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), 124.3 0(d,J=47.3Hz),122.56(d,J=38.4Hz),121.16,118.06,116.69(d,J=47.1Hz),116.69,115.98(d,J =91.0Hz), 115.83 (d, J = 1.9Hz), 112.30, 108.75, 74.98, 72.01, 34.52, 34.45, 31.94, 31.72, 25.71.

[0604] Example 102: Synthesis of Main Catalyst 48

[0605]

[0606] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, a transparent, colorless solution of anhydrous C6D6 (1.37 mL) of thiophene (7.7 mg, 7.48 μmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.19 mL) solution of HfBn4 (4.5 mg, 8.23 ​​μmol, 1.10 equivalent). After stirring (500 rpm) for 30 minutes, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.005 M C6D6 solution. NMR indicated the product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0607] 1H NMR (500MHz, benzene e-d6) δ8.43(dd,J=2.0,0.6Hz,2H),8.29(dd,J=1.9,0.6Hz,2H),7.49(dd,J=8.7,1.9Hz,2H),7.44(dd,J=8.5,1 .9Hz,2H),7.24(dd,J=8.7,0.6Hz,2H),7.19(dd,J=8.5,0.6Hz,2H),7.02–6.96(m,2H),6.94–6.90(m,2H),6.82(s,2H),6.75(t t,J=7.5,1.3Hz,2H),6.55–6.47(m,4H),6.30–6.25(m,4H),5.01(dd,J=9.0,4.8Hz,2H),3.89–3.78(m,2H),3.15(dd,J=12.4, 4.7Hz,2H),1.43(s,18H),1.30(s,18H),0.90(d,J=13.4Hz,2H),0.73–0.62(m,2H),0.49–0.40(m,2H),0.24(d,J=14.0Hz,2H). 19 F NMR (470 MHz, benzene-d6) δ -115.11–-115.24 (m). 13 C 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, 1 24.55,124.35,122.64,122.33,121.13,118.09,116.76(d,J=23.4Hz),116.46(d,J=23.3Hz) ,116.32,115.52,115.27,112.43,108.74,82.00,78.84,34.52,34.46,31.94,31.72,25.86.

[0608] Example 103: Synthesis of Ligand 23

[0609]

[0610] A mixture of thiopheneboropinacol (1.000 g, 1.104 mmol, 2.70 equiv, 62% NMR purity), K3PO4 (0.703 g, 3.312 mmol, 8.10 equiv), Pd(AmPhos)Cl2 (58.0 mg, 0.0818 mmol, 0.20 equiv), and bisphenyliodonium (0.230 g, 0.4089 mmol, 1.00 equiv) was prepared. The mixture was evacuated and then backfilled with nitrogen three more times, followed by the addition of deoxygenated 1,4-dioxane (8.0 mL) and deoxygenated water (0.8 mL) via syringe. The mixture was then placed in a hood heated to 50°C. After vigorous stirring (1000 rpm) for 40 hours, the black mixture was removed from the hood, allowed to gradually cool to 23°C, filtered with suction onto a pad of silica gel, washed with CHCl (4×20 mL), and the clear black filtrate was concentrated. Residual 1,4-dioxane was removed by rotary evaporation using toluene (2×10 mL). The black mixture was then suspended in CHCl (20 mL) and filtered with suction onto a pad of silica gel, rinsed with CHCl (4×20 mL). The black filtrate was then concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatography purification system; 10%-75% CHCl in hexane to give impure bithiophene (0.232 g) as a light red amorphous foam. NMR indicated the product contained impurities. The impure material was used in subsequent reactions.

[0611] To a solution of the impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) was added concentrated HCl (5 mL) at 23°C under nitrogen. The golden brown solution was stirred (500 rpm) for 20 hours, diluted with 1N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics washed with 1N HCl (1 x 10 mL). The remaining organics were extracted from the aqueous solution with CHCl (2 x 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatography purification system; 10% to 75% CHCl in hexanes afforded the bithiophene (0.143 g, 0.1346 mmol, 33% over two steps) as a white foam. NMR indicated pure product.

[0612] 1H NMR (500MHz, chloroform-d) δ8.15(dd,J=1.9,0.6Hz,4H),7.66(d,J=2.6Hz,2H),7.42(dd,J=8.6,1.9Hz,4H),7.35(s,2H),7.24–7.20(m,4H), 7.18(dd,J=8.7,2.6Hz,2H),7.04(s,2H),6.79(d,J=8.8Hz,2H),4.04(q,J=3.6,2.8Hz,4H),1.91(q,J=2.8,2.4Hz,4H),1.47(s,36H). 13C 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.

[0613] Example 104: Synthesis of Primary Catalyst 49

[0614]

[0615] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.55 mL) transparent colorless solution of thiophene (9.2 mg, 8.66 μmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (4.3 mg, 9.53 μmol, 1.10 equivalent) C6D6 (0.18 mL) solution. After stirring (500 rpm) for 30 minutes, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.0025 M or 0.005 M) directly used for polymerization experiments after filtration.

[0616] 1H NMR (500MHz, benzene-d6) δ8.43(dd,J=2.0,0.6Hz,2H),8.29(dd,J=1.9,0.6Hz,2H),7.53–7.48(m,4H),7.45(dd,J=8.5,1.9Hz ,2H),7.34(dd,J=8.7,0.6Hz,2H),7.31(d,J=2.6Hz,2H),7.22–7.19(m,2H),6.91–6.86(m,2H),6.83(dd,J=8.7,2.7Hz,2 H),6.81(s,2H),6.79–6.74(m,2H),6.24–6.19(m,4H),4.98(d,J=8.7Hz,2H),3.88–3.78(m,2H),3.12(dd,J=11.9,4.7Hz ,2H),1.44(s,18H),1.29(s,18H),0.98(d,J=12.3Hz,2H),0.71–0.64(m,2H),0.53(d,J=12.3Hz,2H),0.53–0.47(m,2H). 13 C NMR (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, 125.1 6,124.69,124.51,124.12,122.73,122.43,121.25,118.17,116.44,115.69,115.54,112.22,108.73,74.66,72.01,34.54,34.46,31.94,31.71,25.77.

[0617] Example 105: Synthesis of the main catalyst 50

[0618]

[0619] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.12 mL) white suspension of thiophene (6.8 mg, 6.40 μmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.16 mL) solution of HfBn4 (3.8 mg, 7.04 μmol, 1.10 equivalent). After stirring (500 rpm) for 30 minutes, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.005 M C6D6 solution. NMR indicated the product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0620] 1 H NMR (400MHz, benzene-d6) δ8.43(d,J=1.9Hz,2H),8.28(d,J=1.8Hz,2H),7.49(dd,J=8.7,1.9Hz,2H),7.43(dd,J=8.6,2.0Hz,2H),7 .31(d,J=2.6Hz,2H),7.24(d,J=8.7Hz,2H),7.17(d,J=8.6Hz,2H),6.98–6.93(m,2H),6.92–6.87(m,2H),6.83(dd,J=8.8,2.7 Hz,2H),6.79(s,2H),6.73(tt,J=7.3,1.3Hz,2H),6.27–6.22(m,4H),4.96(d,J=8.8Hz,2H),3.88–3.76(t,J=10.8Hz,2H),3.1 9–3.06(m,2H),1.43(s,18H),1.28(s,18H),0.89(d,J=13.4Hz,2H),0.70–0.57(m,2H),0.47–0.36(m,2H),0.27–0.20(m,2H). 13 C NMR (101 MHz, benzene-d6) δ 153.93, 152.73, 147.19, 143.50, 143.04, 139.24, 139.01, 138.50, 131.61, 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.

[0621] Example 106: Synthesis of an intermediate of ligand 23

[0622]

[0623] A white heterogeneous mixture of iodophenol (1.604 g, 6.303 mmol, 2.00 equiv), K2CO3 (2.613 g, 18.909 mmol, 6.00 equiv) and 1,4-dibromobutane (0.38 mL, 3.151 mmol, 1.00 equiv) in acetone (60 mL) equipped with a reflux condenser was placed in a mantle heated to 60° C. under nitrogen and removed from the mantle after stirring (500 rpm) for 48 hours. The mixture was homogenized, cooled to 23° C., diluted with CH2Cl2 (50 mL), stirred vigorously (1000 rpm) for 5 minutes, filtered with suction onto a pad of celite, rinsed with CH2Cl2 (3×25 mL), and the resulting filtrate solution was concentrated onto celite and purified by silica gel chromatography; 10% CH2Cl2 in hexanes to 50% CH2Cl2 in hexanes to afford bisiodophenyl ether (1.712 g, 3.041 mmol, 97%) as a white solid. NMR indicated the product.

[0624] 1H NMR (500 MHz, chloroform-d) δ7.73 (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). 13C NMR (126 MHz, chloroform-d) δ156.29, 138.50, 129.17, 126.28, 112.40, 86.72, 69.01, 25.92.

[0625] Example 107: Synthesis of Ligand 24

[0626]

[0627] A mixture of thiopheneboropinacol (1.000 g, 1.104 mmol, 2.70 equiv, 62% NMR purity), K3PO4 (0.703 g, 3.312 mmol, 8.10 equiv), Pd(AmPhos)Cl2 (58.0 mg, 0.0818 mmol, 0.20 equiv), and bisphenyliodonium (0.230 g, 0.4089 mmol, 1.00 equiv) was prepared. The mixture was evacuated and then backfilled with nitrogen three more times, followed by the addition of deoxygenated 1,4-dioxane (8.0 mL) and deoxygenated water (0.8 mL) via syringe. The mixture was then placed in a hood heated to 50°C. After vigorous stirring (1000 rpm) for 40 hours, the black mixture was removed from the hood, allowed to gradually cool to 23°C, filtered with suction onto a pad of silica gel, washed with CHCl (4×20 mL), and the clear black filtrate was concentrated. Residual 1,4-dioxane was removed by rotary evaporation using toluene (2×10 mL). The black mixture was then suspended in CHCl (20 mL) and filtered with suction onto a pad of silica gel, rinsed with CHCl (4×20 mL). The black filtrate was then concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatography purification system; 10%-75% CHCl in hexanes to give impure bithiophene (0.161 g) as a light red amorphous foam. NMR indicated the product contained impurities. The impure material was used in subsequent reactions.

[0628] To a solution of the impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) was added concentrated HCl (5 mL) at 23°C under nitrogen. The golden brown solution was stirred (500 rpm) for 20 hours, diluted with 1N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics washed with 1N HCl (1 x 10 mL). The remaining organics were extracted from the aqueous solution with CHCl (2 x 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatography purification system; 10% to 75% CHCl in hexanes to afford the bithiophene (0.121 g, 0.1139 mmol, 24% over two steps) as a white solid. NMR indicated pure product.

[0629] 1H NMR (500MHz, chloroform-d) δ8.13(d,J=1.9Hz,4H),7.60(d,J=8.3Hz,2H),7.39(dd,J=8.6,1.9Hz,4H),7.31(s,2H),7.20(d,J=8.6H z,4H),7.10(dd,J=8.4,2.0Hz,2H),6.94(d,J=2.0Hz,2H),6.70(s,2H),4.09–4.02(m,4H),1.99–1.90(m,4H),1.44(s,36H). 13 CNMR (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.

[0630] Example 108: Synthesis of Main Catalyst 51

[0631]

[0632] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, anhydrous C6D6 (1.82 mL) transparent colorless solution of thiophene (10.7 mg, 10.10 μmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added ZrBn4 (5.0 mg, 11.10 μmol, 1.10 equivalent) C6D6 (0.20 mL) solution. After stirring (500 rpm) for 30 minutes, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a zirconium complex in a 0.005 M C6D6 solution. NMR indicates product. The same procedure can use toluene as a solvent to prepare the main catalyst solution (0.0025 M or 0.005 M) directly used for polymerization experiments after filtration.

[0633] 1H NMR (500MHz, benzene-d6) δ8.51–8.44(m,4H),8.35–8.26(m,2H),7.63–7.54(m,4H),7.29–7.26(m,2H), 7.14(d,J=8.3Hz,2H),6.94(s,2H),6.91(dd,J=8.3,2.1Hz,2H),6.85–6.77(m,4H),6.51–6.48(m ,4H),6.40–6.32(m,2H),5.86(d,J=2.1Hz,2H),3.48–3.38(m,2H),3.32(m,2H),1.73(d,J=13.1H z,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=13.1Hz,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.

[0634] Example 109: Synthesis of Main Catalyst 52

[0635]

[0636] Before use, the thiophene ligand was dried using toluene (4 × 10 mL) azeotropic drying. At 23 ° C, a transparent colorless solution of anhydrous C6D6 (1.99 mL) of thiophene (12.0 mg, 11.30 μmol, 1.00 equivalent) in a nitrogen-filled glove box was dropwise added to a C6D6 (0.27 mL) solution of HfBn4 (6.8 mg, 12.43 μmol, 1.10 equivalent). After stirring (500 rpm) for 30 minutes, the light golden solution was filtered using a 0.20 μm PTFE submicron filter to obtain a hafnium complex in a 0.005 M C6D6 solution. NMR indicated the product. The same procedure can use toluene as a solvent to prepare a primary catalyst solution (0.005 M) that is directly used in polymerization experiments after filtration.

[0637] 1H NMR (400MHz, benzene-d6) δ8.57(d,J=1.9Hz,2H),8.43–8.38(m,2H),7.60–7.43(m,4H),7.18(d,J=8.6Hz,2H),6.96(d dq,J=7.4,1.4,0.7Hz,4H),6.91–6.85(m,2H),6.81(s,2H),6.82-6.79(m,2H),6.75(tt,J=7.3,1.2Hz,2H),6.66 (dd,J=8.4,2.1Hz,2H),6.50–6.45(m,4H),5.54(d,J=2.1Hz,2H),3.66–3.53(m,2H),2.90–2.83(m,2H),1.33(s, 18H),1.22(s,18H),1.05(dd,J=13.4,5.9Hz,2H),0.91–0.71(m,2H),0.55–0.40(m,2H),0.34(d,J=13.6Hz,2H).

[0638] Example 110: Synthesis of an intermediate of ligand 24:

[0639]

[0640] A white heterogeneous mixture of iodophenol (2.475 g, 9.727 mmol, 2.00 equiv), K2CO3 (4.033 g, 29.180 mmol, 6.00 equiv) and 1,4-dibromobutane (0.58 mL, 4.864 mmol, 1.00 equiv) in acetone (100 mL) equipped with a reflux condenser was placed in a mantle heated to 60°C under nitrogen. The white heterogeneous mixture was removed from the mantle after stirring (500 rpm) for 36 hours. The homogeneous mixture was cooled to 23° C., diluted with CH 2 Cl 2 (50 mL), stirred vigorously (1000 rpm) for 5 minutes, filtered with suction onto a pad of celite, rinsed with CH 2 Cl 2 (3×25 mL), and the resulting filtrate solution was concentrated onto celite and purified by silica gel chromatography; 10% CH 2 Cl 2 in hexanes to 50% CH 2 Cl 2 in hexanes to give bisiodophenyl ether (2.456 g, 4.362 mmol, 90%) as a white solid. NMR indicated the product.

[0641] 1 H 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). 13CNMR (101 MHz, chloroform-d) δ 158.00, 139.68, 135.13, 122.49, 112.66, 83.83, 68.90, 25.86.

[0642] Example 111 - Polymer Produced from Primary Catalyst

[0643] The catalyst efficiency (gram polymer yield / gram metal) and the resulting polymer properties of procatalysts 1-52 were evaluated. Polymerization reactions were carried out in a 2-L semi-batch reactor initially without diethylzinc (DEZ) and then with the addition of three different loadings of DEZ (0 μmol, 50 μmol, and 200 μmol). The activator was 1.5 molar equivalents of bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyl)ammonium borate. Prior to the polymerization experiments, procatalysts 7, 8, 11, and 12 were premixed in a 0.005 M solution with an excess of MMAO-3A (10.0 equivalents) for 10 minutes.

[0644] The procatalysts in Table 1 are capable of producing polymers at temperatures up to 190°C with a range of low to high efficiencies (grams polymer / gram metal). The highest catalyst processing efficiencies are observed when the procatalysts have unsubstituted or substituted carbazole substituents with the oxygen forming the covalent bond to the metal center in the ortho position, as observed for the procatalysts 5, 6, 13, and 30 in the Examples. The highest molecular weight capabilities are observed when the 3,5-di-tert-butylphenyl, 3,6-bis-(2,4,6-triisopropylphenyl)carbazole, and 3,6-di-tert-butylcarbazole substituents are in the ortho position to the anion donor, as observed for procatalysts 5, 6, 13, and 30 in the Examples. In general, under these reactor conditions, these catalysts produce polymers with narrow PDI (<4) and mid-range to high comonomer incorporation (5%-21%).

[0645] Table 1: Polymerization data for semi-batch reactor experiments

[0646]

[0647]

[0648]

[0649] The standard semi-batch reactor conditions for the polymerization results at 120°C in Table 1 contained 46 g ethylene and 303 g 1-octene in 611 g Isopar E. The standard semi-batch reactor conditions for the polymerization results at 150°C in Table 1 contained 43 g ethylene and 303 g 1-octene in 547 g Isopar E. The standard semi-batch reactor conditions for the polymerization results at 190°C in Table 1 contained 46 g ethylene and 292 g 1-octene in 515 g Isopar E. *Mol % octene or C8 / olefin is defined as: (mole 1-octene / (total moles of 1-octene and ethylene)) x 100. ND = Not Determined.

[0650] To determine the chain transfer rate of the more efficient procatalyst, semi-batch runs were performed using varying amounts of the chain transfer agent Et2Zn (0 μmole, 50 μmole, and 200 μmole). All reactions were performed at 120°C or 150°C using 1.2 equivalents of bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate as an activator. Procatalysts 7, 8, 11, and 12 were premixed with excess MMAO-3A (10.0 equivalents) in a 0.005 M solution for 10 minutes prior to polymerization. Batch runs were performed at 120°C or 150°C using 11.1 g or 12.1 g of ethylene, 56 g or 57 g of 1-octene, and 528 g or 555 g of Isopar E at 76-136 psi. The catalyst efficiencies and the corresponding Mw, PDI, and comonomer incorporation of the resulting polymers are presented in Table 2.

[0651] Table 2: Polymerization data for semi-batch reactor experiments with Et2Zn(DEZ)

[0652]

[0653]

[0654]

[0655]

[0656] The standard semi-batch reactor conditions for the polymerization results at 120°C in Table 2 contained 11 g ethylene and 59 g 1-octene in 610 g Isopar E. The standard semi-batch reactor conditions for the polymerization results at 150°C in Table 2 contained 12 g ethylene and 59 g 1-octene in 531 g Isopar E. *Mol % octene or C8 / olefin is defined as: (moles of 1-octene / (total moles of 1-octene and ethylene)) x 100.

[0657] Calculate M for each run using Equation 3 n, where Ca and M are fitted using Microsoft Excel Solver n0 The value of is chosen to minimize the squared deviation between the fitted and experimental molecular weight data for all runs performed with a particular catalyst. Figure 5 Shows M n A graph showing the [CSA] of the main catalysts 1-7 and 9-52, including the graph showing M n The line of expected dependence of [CSA] from the best-fit value of Ca and the calculated Ca values ​​are presented in Table 3.

[0658] Table 3: Chain transfer rates for semi-batch reactor experiments with Et2Zn(DEZ)

[0659]

[0660] The high chain transfer constants (Ca ≥ 1) for many of the procatalysts at 120° C. and 150° C. indicate that these catalysts are highly sensitive to chain transfer agents and rapidly undergo chain transfer by these agents. Overall, similar or decreasing PDI values ​​were observed for each procatalyst (except procatalysts 2, 12, and 51) as the amount of Et2Zn increased, demonstrating that these procatalysts undergo reversible chain transfer by CSA rather than irreversible chain transfer.

Claims

1. A catalyst system comprising: A metal-ligand complex selected from any one of the following procatalysts: and a chain transfer agent comprising a trialkylaluminum and a dialkylzinc.

2. A process for polymerizing an ethylene-based polymer, said process comprising reacting ethylene with one or more C1-C 20 α-olefin contact.

Images