Group IV transition metal polymerization of biarylhydroxythiophenes with chain transfer capability.

Abstract

An embodiment of the present disclosure includes a polymerization process comprising contacting propylene and / or one or more (C4-C12) α-olefins in a reactor containing a catalyst system comprising a metal-ligand complex according to formula (I). [Formula 1] JPEG2022524504000137.jpg90170

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 815,567, filed March 8, 2019, the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to propylene polymerization catalyst systems and processes, and more specifically to the synthesis of biarylphenoxy Group IV transition metal catalysts for propylene polymerization and olefin polymerization processes incorporating the catalyst systems. [Background technology]

[0003] Olefin-based polymers, such as polypropylene and propylene-based polymers, are produced by a variety of catalyst systems. The selection of such catalyst systems used in olefin-based polymer polymerization processes is an important factor contributing to the characteristics and properties of such olefin-based polymers. Many catalysts that efficiently produce ethylene-based polymers are substantially less effective in producing polypropylene.

[0004] Polypropylene-based polymers are produced for a wide variety of products. By varying the parameters of the polypropylene polymerization process, polypropylene resins can be tailored to have physical properties that are compatible with the resin's use in a desired application. In the polymerization reactor, propylene monomer and optionally one or more comonomers are present in a diluent or solvent. Examples of diluents or solvents include alkanes or isoalkanes, such as isobutane. Hydrogen can also be added to the reactor. Typical catalyst systems for producing propylene-based polymers may include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or metallocene or nonmetallocene molecular transition metal catalyst systems. The reactants and catalyst system in the diluent are circulated in the reactor at elevated polymerization temperatures, thereby producing a propylene-based homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture, including the polypropylene product dissolved in the diluent, is removed from the reactor along with unreacted polypropylene and one or more optional comonomers. Upon removal from the reactor, the reaction mixture may be treated to remove the polypropylene product from the diluent and unreacted reactants, which are typically recycled back into the reactor. Alternatively, the reaction mixture may be sent to a second reactor connected in series with the first reactor, where a second polypropylene fraction may be produced. Summary of the Invention [Problem to be solved by the invention]

[0005] Despite the current availability of olefin polymerization catalyst systems in homogeneous solution, there is a need for catalysts that can polymerize propylene using chain transfer and chain shuttling agents (CSAs) to produce polypropylenes with various stereoregularities and molecular weights, as well as olefin block copolymers (OBCs) containing polypropylene units.

[0006] Embodiments of the present disclosure include a polymerization process comprising the polymerization of propylene and any one or more (C4-C6) olefins in a reactor in the presence of a catalyst system. 12) an α-olefin. The catalyst system comprises a metal-ligand complex according to formula (I): [ka]

[0007] 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 independently an unsaturated (C2-C 20 ) Hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (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 (X) is a monodentate or bidentate ligand selected from n The subscript n is 1 or 2. Each Y is -O-, -S-, or -N(R N )-.

[0008] In formula (I), each R 1 are independently -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C)2NC(O)-, a halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV). [ka]

[0009] In formulas (II), (III) and (IV), R 31~35 , R 41~48 , and R 51~59 Each of the is independently (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)—, halogen or —H, provided that at least one R in formula (I) 1 is a radical having formula (II), a radical having formula (III), or a radical having formula (IV).

[0010] In formula (I), Q is (C1-C 12 ) alkylene, (C1-C 12 ) heteroalkylene, (-CH2Si(R Q )2CH2-), (-CH2CH2Si(R Q )2CH2CH2-), (-CH2Ge(R Q )2CH2-) or (-CH2CH2Ge(R Q )2CH2CH2-) in which R Q (C1-C 20) hydrocarbyl. Each z1 and z2 is independently sulfur, oxygen, —N(R Z )-, and -C(R Z )-, with the proviso that in each individual ring containing groups z1 and z2, at least one of z1 and z2 is sulfur.

[0011] In formula (I), R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b , and R 7b are independent, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C 6- C 50 ) aryl, (C4-C 50 ) heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, -P(O)(R P )2, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, and -H. Optionally, R 4a and R 5a , or R 5a and R 6a , or R 6a and R 7a , or R 4b and R 5b , or R 5b and R 6b , or R 6b and R 7b may be covalently linked to form an aromatic or non-aromatic ring.

[0012] Each R in formula (I) C , R N , R Z and R P are independent, (C1-C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl and —H. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 shows Ligand 1 to Ligand 10. [Figure 2] FIG. 2 shows Ligands 11 to 19. [Figure 3] FIG. 3 shows Ligands 20 to 25. [Figure 4] FIG. 4 shows a three-step synthetic scheme for synthesizing the precursor of the ligand. [Figure 5] FIG. 5 shows a three-step synthetic scheme for synthesizing the precursor of the ligand. DETAILED DESCRIPTION OF THE INVENTION

[0014] Specific embodiments of the catalyst system are described below. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments described in this disclosure.

[0015] Common abbreviations are listed below.

[0016] R, Z, M, X and n: as defined above, Me: methyl, Et: ethyl, Ph: phenyl, Bn: benzyl, i-Pr: isopropyl, t-Bu: tert-butyl, t-Oct: tert-octyl(2,4,4-trimethylpentan-2-yl), Tf: trifluoromethanesulfonate, CV: column volume (used in column chromatography), EtOAc: ethyl acetate, TEA: triethylaluminum, MAO: methylaluminoxane, MMAO: modified methylaluminoxane, LiCH2TMS: (trimethylsilyl)methyllithium, TMS: trimethylsilyl, Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II), Pd(AmPhos): chloro(crotyl)(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II), Pd(dppf ) Cl2: [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride, ScCl3: scandium(III) chloride, PhMe: toluene, THF: tetrahydrofuran, CHCl2: dichloromethane, DMF: N,N-dimethylformamide, EtOAc: ethyl acetate, Et2O: diethyl ether, MeOH: methanol, NHCl: ammonium chloride, MgSO4: magnesium sulfate, NaSO4: sodium sulfate, NaOH: sodium hydroxide, Brine: saturated aqueous sodium chloride, SiO2: silica, CDCl3: chloroform-D, GC: gas chromatography, LC: liquid chromatography, NMR: nuclear magnetic resonance, MS: mass spectrometry, mmol: millimole, mL: milliliter, M: mole, min or mins: minute, h or hrs: hour, d: day, TLC: thin layer chromatography, rpm: revolutions per minute, rt: room temperature.

[0017] The term "independently selected" refers to 1 , R 2 , R 3 , R 4 , and R 5 and the R groups may be the same or different (e.g., R 1 , R 2 , R 3 , R4 , and R 5 may all be substituted alkyl, or R 1 and R 2 may be substituted alkyl, R 3 The R group is used herein to indicate that the R group may be an aryl group, etc. Chemical names associated with R groups are intended to convey chemical structures recognized in the art as corresponding to the chemical structure of the chemical name. Thus, the chemical names are intended to supplement and illustrate, not preclude, structural definitions known to those of skill in the art.

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

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

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

[0021] In the present disclosure, (C1-C 50 ) hydrocarbyl is unsubstituted or substituted (C-C 50 ) alkyl, (C3-C 50 ) cycloalkyl, (C3-C 20 )Cycloalkyl-(C1-C 20 ) alkylene, (C6-C 40 ) aryl, or (C6-C 20 )Aryl-(C1-C 20) alkylene, such as benzyl (—CH2—C6H5).

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

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

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

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

[0026] "(C1-C 50 The term "alkylene" refers to an unsubstituted or substituted group with one or more R Smeans a saturated straight or branched chain diradical (i.e., the radical is not on a ring atom) having 1 to 50 carbon atoms substituted by 50 Examples of alkylene are unsubstituted (C-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), where “C*” represents a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. 50 Examples of alkylenes are substituted (C-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosylene). As mentioned above, the two R S are combined together, (C1-C 18 ) alkylene, so that substituted (C1-C 50 Examples of )alkylene also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

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

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

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

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

[0031] "(C1-C50 The term "(C1-C2) heteroalkyl" means a saturated straight or branched chain radical containing 1 to 50 carbon atoms and one or more heteroatoms. 50 The term "heteroalkylene" refers to a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of a heteroalkyl or heteroalkylene include Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C , S, S.R. C , S(O), and S(O), each of the heteroalkyl and heteroalkylene groups may be unsubstituted or may contain one or more R S has been replaced by

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

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

[0034] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted by, one or more double and / or triple bonds may optionally be substituted by a substituent R S The term "unsaturated" refers to a group containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or carbon-silicon double bonds, and the substituent R S This means that the aromatic ring or heteroaromatic ring does not contain any double bonds that may be present in the ring (if present), or in the aromatic or heteroaromatic ring (if present).

[0035] Some embodiments of the present disclosure include a polymerization process. The polymerization process comprises the polymerization of propylene and any one or more (C4-C6) olefins in a reactor in the presence of a catalyst system and a transfer agent. 12 ) an α-olefin. The catalyst system comprises a metal-ligand complex according to formula (I): [ka]

[0036] 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 independently an unsaturated (C2-C 20 ) Hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (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 (X) is a monodentate or bidentate ligand selected from n The subscript n is either 1 or 2.

[0037] In formula (I), each R 1 are independently -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, a halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV). [ka]

[0038] In formulas (II), (III) and (IV), each R 31~35 , R 41~48 , and R 51~59 are independent, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C)2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)—, halogen or —H, provided that at least one R in formula (I) 1 is a radical having formula (II), a radical having formula (III), or a radical having formula (IV).

[0039] In formula (I), Q is (C1-C 12 ) alkylene, (C1-C 12 ) heteroalkylene, (C1-C 20 ) arylene, (C1-C 20 ) heteroarylene, (-CH2Si(R Q )2CH2-), (-CH2CH2Si(R Q )2CH2CH2-), (-CH2Ge(R Q )2CH2-) or (-CH2CH2Ge(R Q )2CH2CH2-) in which R Q (C1-C 20 ) hydrocarbyl. Each z1 and z2 is independently sulfur, oxygen, —N(R Z )-, and -C(R Z )-, with the proviso that in each individual ring containing groups z1 and z2, at least one of z1 and z2 is sulfur.

[0040] In formula (I), R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b and R 7b are independent, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C 6- C 50 ) aryl, (C4-C 50 ) heteroaryl, -Si(R C )3, -Ge(RC )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, -P(O)(R P )2, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, and -H. Optionally, R 4a and R 5a , or R 5a and R 6a , or R 6a and R 7a , or R 4b and R 5b , or R 5b and R 6b , or R 6b and R 7b may be covalently linked to form an aromatic or non-aromatic ring.

[0041] Each R in formula (I) C , R N , R Z and R P are independent, (C1-C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl and —H.

[0042] In some embodiments, each z1 is sulfur and z2 is —C(R Z )-, wherein R Z is (C1-C8) alkyl or —H. In other embodiments, each z2 is sulfur and z1 is —C(R Z )-, wherein R Z is (C1-C8) alkyl or -H.

[0043] In one or more embodiments of the metal-ligand complex of formula (I), each R 1is a radical having formula (III), where R 41~48 At least one of (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -OR C , -SR C , —NO2, —CN, —CF3, or halogen. In various embodiments of the metal-ligand complex of formula (I), each R 1 is a radical having formula (III), where R 42 and R 47 is (C1-C 20 ) alkyl, -Si(R C)3 , -CF3 or halogen, and R43 and R 46 is —H. In other embodiments, R 43 and R 46 are independent, (C1-C 20 ) alkyl, -Si(R C )3, -CF3 or halogen, and R 42 and R 47 is -H.

[0044] In various embodiments of the metal-ligand complex of formula (I), each R 1 is a radical having formula (IV), where R 51~59 At least one of (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -OR C , -SR C , —NO2, —CN, —CF3 or a halogen.

[0045] In one or more embodiments of the metal-ligand complex of formula (I), each R 1 is a radical having formula (II), and R 32 and R 34 are independently (C1-C 40 ) Hydrocarbyl (C1-C 40 ) heterohydrocarbyl, -Si(R C)3, -OR C , -SR C , —NO 2 , —CN, —CF 3 , or halogen. In some embodiments, each R 1 is a radical having formula (II) and R 32 and R 34 are independently (C1-C 20 ) alkyl, substituted (C6-C 20 ) aryl or unsubstituted (C6-C 20 ) aryl. In various embodiments, each R 1 is a radical having formula (II) and R 32 and R 34 is independently tert-butyl, phenyl, 3,5-di(tert-butyl)phenyl, 2,4,6-trimethylphenyl, or 2,4,6-tri(isopropyl)phenyl.

[0046] In some embodiments of the metal-ligand complex of formula (I), R 4a , R 5a , R 6a , R 7a At least one of R is halogen; 4b , R 5b , R 6b and R 7b At least one of R is halogen. 4a , R 5a , R 6a , R 7a At least two of R are halogens, 4b , R 5b , R 6b and R 7b At least two of R are halogen. 4a , R 5a , R 6a , R 7a At least three of the R 4b , R 5b , R 6b and R 7b At least three of the groups are halogens.

[0047] In one or more embodiments of the metal-ligand complex of formula (I), Q is (—CHSi(R Q )2CH2-), (-CH2CH2Si(R Q )2CH2CH2-), (-CH2Ge(R Q )2CH2-) or (-CH2CH2Ge(R Q )2CH2CH2-) in which R Q is (C1-C5) alkyl. In other embodiments, Q is benzene-1,2-diyl or cyclohexane-1,2-diyl. In some embodiments, Q is (-CH2Si(R Q )2CH 2- ) or (-CH2Si(R Q )2CH 2- ) where R Q is ethyl or 2-propyl. In one or more embodiments, Q is benzene-1,2-diyldimethyl.

[0048] In one or more embodiments of the metal-ligand complex of formula (I), when Q is (C-C) alkylene, R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b and R 7b At least two of them are (C6-C 50 ) aryl, (C4-C 50 ) heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, -P(O)(R P )2, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C)2NC(O)— and halogen.

[0049] In one or more embodiments of the metal-ligand complex of formula (I), each Y is —O—, —S—, or —N(R N )-. In some embodiments, Y is oxygen.

[0050] In one or more embodiments, the polymerization process of the present disclosure comprises the step of polymerizing propylene and / or one or more (C-C) olefins in a reactor in the presence of a catalyst system and a chain transfer or chain shuttle agent. 12 The polymerization process comprises contacting an α-olefin with a mixture or reaction product of: (A) a procatalyst and a cocatalyst comprising a metal-ligand complex having the structure of formula (I), (B) an olefin polymerization catalyst characterized by having a comonomer selectivity different from that of the procatalyst of (A), and (C) a chain transfer or chain shuttle agent.

[0051] As used herein, the term "chain transfer agent" refers to a molecule capable of transferring polymer chains between two separate catalysts within a single polymerization reactor. Each catalyst within the reactor may have a different monomer selectivity. While the term "chain transfer agent" is similar to the term "chain shuttle agent," those skilled in the art will recognize that chain transfer agents can be used as chain shuttle agents depending on the type of reactor and catalyst system. For example, chain shuttle occurs in a continuous reactor with a dual catalyst system. In this scenario, the chain shuttle agent is added to the catalyst system of the polymerization reaction. In contrast, chain transfer occurs in a batch reactor with a single catalyst system, so the chain transfer agent is added to the catalyst system. However, the same molecule can be used as either a chain transfer agent or a chain shuttle agent.

[0052] Typically, the chain transfer agent comprises a first metal that is Al, B, or Ga, wherein the first metal is in a formal oxidation state of +3, or a second metal that is Zn or Mg, wherein the second metal is in a formal oxidation state of +2. Chain transfer agents are described in U.S. Patent Application Publication No. 2007 / 0167315, which is incorporated herein by reference in its entirety.

[0053] In one or more embodiments of the polymerization process, the chain transfer agent, if present, is selected from the group consisting of diethyl zinc, di(iso-butyl) zinc, di(n-hexyl) zinc, triethyl aluminum, trioctylaluminum, triethylgallium, iso-butylaluminum bis(dimethyl(t-butyl)siloxane), iso-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxy), bis(n-octadecyl)iso-butylaluminum, iso-butylaluminum bis(di(n-pentyl)amide), n-octylaluminum bis(2,6-di-t-butylphenoxide ... may be selected from aluminum di(ethyl(l-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminum bis(2,3,6,7-dibenzo-l-azacycloheptanamide), n-octylaluminum bis(2,3,6,7-dibenzo-l-azacycloheptanamide), n-octylaluminum bis(dimethyl(dimethyl)t-butyl)siloxide, ethylzinc(2,6-diphenylphenoxide), ethylzinc(t-butoxide), dimethylmagnesium, dibutylmagnesium and n-butyl-sec-butylmagnesium.

[0054] In an exemplary embodiment, the catalyst system can include a metal-ligand complex according to Formula (I) having any of the structures of Procatalysts 1-28. [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0055] Co-catalyst component Catalyst systems containing the metal-ligand complexes of formula (I) can be catalytically activated by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, procatalysts based on the metal-ligand complexes of formula (I) can be catalytically activated by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. Furthermore, metal-ligand complexes based on formula (I) include both neutral procatalyst forms and catalyst forms that can be positively charged by loss of monoanionic ligands such as benzyl, methyl, or phenyl. Activating cocatalysts suitable for use herein include alkylaluminums, polymeric or oligomeric alumoxanes (also known as aluminoxanes), neutral Lewis acids, and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the aforementioned activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means a monoalkylaluminum dihydride or dihalide, a dialkylaluminum hydride or halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0056] The Lewis acid activating cocatalyst may be any of the compounds described herein (C1-C 20 In some embodiments, the Group 13 metal compound includes a tri((C-C) hydrocarbyl substituent. 20 )hydrocarbyl)-substituted aluminum or tri((C-C 20 In other embodiments, the Group 13 metal compound is a tri(hydrocarbyl)-substituted aluminum, tri((C-C 20 )hydrocarbyl)-boron compounds, tri((C-C 10 ) alkyl) aluminum, tri((C6-C 18 )aryl)boron compounds and their halogenated (including perhalogenated) derivatives. In further embodiments, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C-C 20 ) hydrocarbyl borates (e.g., trityl tetrafluoroborate) or tri((C-C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)boranes (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to a ((C-C 20 ) Hydrocarbyl) 4N + , ((C1-C 20 )hydrocarbyl)3N(H) + , ((C1-C 20 )hydrocarbyl)2N(H)2 + , (C1-C 20 ) Hydrocarbyl N(H)3 + , or N(H)4 + means a nitrogen cation, each (C1-C 20 ) When two or more hydrocarbyls are present, they may be the same or different.

[0057] A combination of neutral Lewis acid activating cocatalysts is tri((C1-C4) alkyl)aluminum and tri((C6-C 18 )aryl)boron compounds, particularly tris(pentafluorophenyl)borane. Other embodiments include mixtures containing such neutral Lewis acid mixtures with polymeric or oligomeric alumoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymeric or oligomeric alumoxanes. The molar ratio of (metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane)] is 1:1:1 to 1:10:30, and in other embodiments, 1:1:1.5 to 1:5:10.

[0058] A catalyst system comprising the metal-ligand complex of formula (I) can be activated to form an active catalyst composition by combining it with one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, as well as 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.

[0059] In some embodiments, two or more of the aforementioned activating cocatalysts can be used in combination with one another. A specific example of a cocatalyst combination is a mixture of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of the total number of moles of the one or more metal-ligand complexes of Formula (I) to the total number of moles of the one or more activating cocatalysts is 1:10,000 to 100:1. In some embodiments, this ratio is at least 1:5000, in other embodiments at least 1:1000, and 10:1 or less, and in still other embodiments, 1:1 or less. When alumoxane is used alone as the activating cocatalyst, the number of moles of alumoxane used is preferably at least 100 times the number of moles of the metal-ligand complex of Formula (I). When tris(pentafluorophenyl)borane is used alone as the activating cocatalyst, in some other embodiments, the ratio of moles of tris(pentafluorophenyl)borane in the reaction to the total moles of one or more metal-ligand complexes of Formula (I) is 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1. The remaining activating cocatalyst is generally used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of Formula (I).

[0060] Polyolefin The aforementioned catalyst system is utilized for the polymerization of olefins, primarily propylene. In some embodiments, only a single type of olefin, or α-olefin, is present during the polymerization process, producing a homopolymer. However, additional α-olefins may be incorporated into the polymerization process. The additional α-olefin comonomer typically has 20 or fewer carbon atoms. For example, the α-olefin comonomer may have 3 to 10 carbon atoms, or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene.

[0061] Propylene-based polymers, such as homopolymers of propylene and / or interpolymers (including copolymers) of propylene and any one or more comonomers, such as α-olefins, can contain at least 50 weight percent propylene-derived monomer units. All individual values ​​and subranges encompassed by "from at least 50 weight percent" are disclosed herein as separate embodiments; for example, propylene-based polymers, homopolymers, and / or interpolymers (including copolymers) of propylene and any one or more comonomers, such as α-olefins, can contain at least 60 weight percent propylene-derived monomer units, at least 70 weight percent propylene-derived monomer units, at least 80 weight percent propylene-derived monomer units, 50 to 100 weight percent propylene-derived monomer units, or 80 to 100 weight percent propylene-derived monomer units.

[0062] In some embodiments, the propylene-based polymer can comprise at least 90 mole percent propylene-derived units. All individual values ​​and subranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, the propylene-based polymer can comprise at least 93 mole percent propylene-derived units, at least 96 mole percent units, at least 97 mole percent propylene-derived units, or alternatively, 90 to 100 mole percent propylene-derived units, 90 to 99.5 mole percent propylene-derived units, or 97 to 99.5 mole percent propylene-derived units.

[0063] In some embodiments of the propylene-based polymer produced by the polymerization process of the present disclosure, the amount of additional α-olefin is less than 50 mol %, other embodiments include at least 0.5 mol % to 25 mol %, and in further embodiments, the amount of additional α-olefin is at least 5 mol % to 10 mol %. In some embodiments, the additional α-olefin is 1-octene.

[0064] The polymerization process according to the embodiment may include components, aspects, or equipment of a conventional polymerization process for producing a propylene-based polymer, provided that the conventional process further includes a catalyst system comprising a metal-ligand complex according to formula (I) of the present disclosure. Such conventional polymerization processes include, but are not limited to, solution polymerization processes, gas-phase polymerization processes, slurry-phase polymerization processes, and any combination thereof, using a parallel or series combination of one or more conventional reactors. Such conventional reactors include, for example, loop reactors, isothermal reactors, fluidized-bed gas-phase reactors, stirred-tank reactors, batch reactors, or any combination thereof.

[0065] In one embodiment, a propylene-based polymer can be produced by solution polymerization in a dual reactor system, for example, a dual loop reactor system, where propylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein and optionally one or more cocatalysts. In another embodiment, a propylene-based polymer can be produced by solution polymerization in a dual reactor system, for example, a dual loop reactor system, where propylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein and optionally one or more other catalysts. The catalyst system described herein can be used in the first reactor or the second reactor, optionally in combination with one or more other catalysts. In one embodiment, a propylene-based polymer can be produced by solution polymerization in a dual reactor system, for example, a dual loop reactor system, where propylene and optionally one or more α-olefins are polymerized in both reactors in the presence of the catalyst system described herein.

[0066] In another embodiment, a propylene-based polymer can be produced by solution polymerization in a single reactor system, for example a single loop reactor system, where propylene, and optionally one or more α-olefins, are polymerized as described in the previous paragraph in the presence of a catalyst system described within this disclosure and optionally one or more cocatalysts.

[0067] The propylene-based polymer may further comprise one or more additives introduced into the reactor at an appropriate stage during the polymerization process. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The propylene-based polymer may contain any amount of additives. The propylene-based polymer may comprise from about 0 to about 10 percent total weight of such additives, based on the weight of the propylene-based polymer and one or more additives. The propylene-based polymer may further comprise a filler, including, but not limited to, an organic or inorganic filler. The propylene-based polymer may contain from about 0 to about 20 percent by weight of a filler, such as calcium carbonate, talc, or Mg(OH)2, based on the total weight of the propylene-based polymer and all additives or fillers. The propylene-based polymer may be further mixed with one or more polymers to form a blend.

[0068] In some embodiments, a polymerization process for producing a propylene-based polymer can include polymerizing propylene and at least one additional α-olefin in the presence of a catalyst system incorporating at least one metal-ligand complex of formula (I). Polymers obtained from such catalyst systems incorporating a metal-ligand complex of formula (I) can have a densitometric value of, for example, 0.850 g / cm according to ASTM D792, which is incorporated herein by reference in its entirety. 3 ~0.950g / cm 3 , 0.880g / cm 3 ~0.920g / cm 3 , 0.880g / cm 3 ~0.910g / cm 3 , or 0.880 g / cm 3 ~0.900g / cm 3 The density may be

[0069] In another embodiment, the polymer resulting from the catalyst system comprising the metal-ligand complex of formula (I) has a melt flow ratio (I 10 / I2), where the melt index I2 is measured at 230°C and a load of 2.16 kg according to ASTM D1238 (which is incorporated herein by reference in its entirety), and the melt index I 10 is measured according to ASTM D1238 at 230°C and a load of 10 kg. In other embodiments, the melt flow ratio (I 10 / I2) is 10-100, and in others, the melt flow ratio is 10-80.

[0070] In some embodiments, the polymer obtained from the catalyst system comprising the metal-ligand complex of formula (I) has a molecular weight distribution (MWD) of 2.0 to 20, w / M n is defined as M w is the weight average molecular weight, and M n is the number average molecular weight. All individual values ​​and subranges encompassed by "2.0 to 20" are disclosed herein as separate embodiments; for example, the polymer resulting from the catalyst system has an MWD of 2.0 to 6. Another embodiment includes an MWD of 2.0 to 5.5, and another embodiment includes an MWD of 2 to 3.

[0071] Embodiments of the catalyst systems described in this disclosure result in unique polymer properties as a result of the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

[0072] Experimental procedure All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passage through activated alumina and, in some cases, Q-5 reactants. Solvents used in experiments conducted in a nitrogen-filled glovebox were further dried by storage over activated 4 Å molecular sieves. Moisture-sensitive reaction glassware was dried overnight in an oven before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analysis was performed using a Waters e2695 separations module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation is performed on an XBridge C18 3.5 μm 2.1 × 50 mm column using a 5:95 to 100:0 gradient of acetonitrile and water (with 0.1% formic acid as the ionizing agent). HRMS analysis is performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column coupled to an Agilent 6230 TOF mass spectrometer equipped with electrospray ionization. 1 H NMR data are reported as follows: chemical shifts (multiplicities (br = broad line, s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, sex = sextet, sept = septet, and m = multiplet), integrals, and assignments). Using residual protons in deuterated solvents as reference standards, 1 Chemical shifts for 1 H NMR data are reported in ppm downfield from internal tetramethylsilane (TMS, δ scale). 13 C NMR data is 1 Determined with 1 H decoupling, chemical shifts are reported as ppm downfield from tetramethylsilane (TMS, δ scale) using residual carbon in the deuterated solvent as the reference.

[0073] General procedure for parallel pressure reactor screening experiments Polyolefin catalyst screening is performed in a high-throughput parallel pressure reactor (PPR) system. The PPR system consists of an array of 48 single-cell (6 × 8 matrix) reactors within an inert atmosphere glovebox. Each cell is equipped with a glass insert with an internal working liquid volume of approximately 5 mL. Each cell has independent pressure control, and the liquid within the cell is continuously stirred at 800 rpm. Catalyst solutions are prepared by dissolving the appropriate amount of procatalyst in toluene, unless otherwise noted. All liquids (e.g., chain shuttle agent solution appropriate for solvent experiments, and catalyst solution) are added to the single-cell reactors via robotic syringes. Gaseous reagents (i.e., propylene, H2) are added to the single-cell reactors via gas injection ports. Before each run, the reactors are heated to 80 °C, purged with propylene, and vented.

[0074] A portion of Isopar-E is added to the reactor. The reactor is heated to the operating temperature and pressurized with propylene to the appropriate psig. A toluene solution of the reagents is added in the following order: (1) 500 nmol of scavenger MMAO-3A, ​​(2) activator (Cocatalyst-1, Cocatalyst-2, etc., 1.50 equivalents relative to the precatalyst), and (3) catalyst.

[0075] A small amount of Isopar-E is added after each liquid addition, ensuring a total reaction volume of 5 mL after the final addition. Once the catalyst is added, the PPR software begins monitoring the pressure in each cell. Pressure (within approximately 2-6 psig) is maintained by adding additional propylene gas by opening the valve at 1 psi below the setpoint and closing the valve when the pressure rises above 2 psi. All pressure drops are cumulatively recorded as propylene "uptake" or "conversion" over the run period, or until the desired uptake or conversion value is reached, whichever occurs first. Each reaction is quenched by adding 10% carbon monoxide in argon for 4 minutes at a pressure 40-50 psi above the reactor pressure. A shorter "quench time" indicates a more active catalyst. To prevent excessive polymer formation in any given cell, reactions are quenched when a predetermined uptake level (70 psig for a run at 110 °C) is reached. After all reactions are quenched, the reactor is cooled to 70 °C. The reactor was vented and purged with nitrogen for 5 minutes to remove carbon monoxide, and the tube was removed. The polymer sample was dried in a centrifugal evaporator at 70°C for 12 hours, weighed, and subjected to IR (1-octene incorporation) and GPC (molecular weight) analysis to determine the polymer yield.

[0076] HT-GPC analysis Molecular weight data are determined by analysis on a hybrid Symyx / Dow-built robot-assisted dilution high-temperature gel permeation chromatography instrument (Sym-RAD-GPC). Polymer samples are dissolved by heating at 160°C for 120 minutes in 1,2,4-trichlorobenzene (TCB) at a concentration of 10 mg / mL, stabilized with 300 parts per million (ppm) butylated hydroxyltoluene (BHT). Each sample was diluted to 1 mg / mL immediately before injection of a 250 μL aliquot. The GPC is equipped with two Polymer Labs PLgel 10 μm mixed-B columns (300 × 10 mm) at 160°C and a flow rate of 2.0 mL / min. Sample detection is performed using a PolyChar IR4 detector in concentration mode. Conventional calibration values ​​of narrow polystyrene (PS) standards are converted and applied as homopolypropylene (PP) apparent units using known Mark-Houwink coefficients for PS and PP in TCB at this temperature.

[0077] DSC analysis Differential scanning calorimetry (DSC) was used to determine the melting transition temperature (T M ) was measured. A TA Instruments Discovery DSC was used for the DSC measurements. Using the "Jump To" function, the sample was first heated from room temperature to 175°C. After holding at this temperature for 3 minutes, the sample was cooled to 0°C at 30°C / min and then reheated to 175°C at 10°C / min. T M Values ​​were measured from this second heating step. [Example]

[0078] Examples 1-113 are synthetic procedures for ligand intermediates, ligands, and isolated procatalysts. Procatalysts 1-50 were synthesized from ligands 1-25 shown in Figures 1-3. Ligands 1-25 were synthesized according to the synthetic schemes shown in Figures 4 and 5.

[0079] Example 1: Synthesis of hydroxy-thiophene intermediate [ka] To a suspension of hydroxythiopene (10.020 grams, 42.267 mmol, 1.00 equiv.) in 1,4-dioxane (100 mL) and HO (450 mL) under nitrogen, NaOH (50.000 g, 1.250 mol, 29.6 equiv.) was added all at once. At this point, the pale yellow mixture was fitted with a reflux condenser and placed in a heated mantle at 80° C. After 2.5 hours of stirring (500 rpm), TLC of the bright yellow solution at this point indicated a lower R of the starting thiophene. f The reaction mixture showed complete conversion to a spot. The mixture was removed from the mantle, gradually cooled to 23 °C, and placed in an ice-water bath for 60 min. Concentrated HCl (125 mL, 37%) was added over 10 min. At this point, the white heterogeneous mixture was removed from the ice-water bath and placed in a mantle heated to 60 °C and vigorously stirred (1000 rpm) for 5 h. At this point, the pale yellow solution was removed from the mantle, gradually cooled to 23 °C, diluted with EtO (100 mL), vigorously stirred for 2 min, poured into a separatory funnel, and the layers were separated. The organics were washed with aqueous HCl (2 × 100 mL, 1 N). The remaining organics were extracted from the aqueous layer using EtO (2 × 50 mL), dried over solid NaSO, decanted, and the EtO was removed by rotary evaporation to give the crude bromo-hydroxythiophene as a solution in 1,4-dioxane (100 mL). An aliquot was removed and concentrated completely under reduced pressure; NMR analysis indicated the pure product, present as a mixture of tautomers. This material is used in subsequent experiments without further concentration or purification.

[0080] A clear, pale yellow solution of hydroxythiophene in 1,4-dioxane (100 mL, as described above) was diluted with non-anhydrous, non-deoxygenated THF (400 mL), HO (6 mL) was added, and the solution was placed in an ice-water bath, sparged with nitrogen for 1 hour, and placed under a positive stream of nitrogen, after which solid lithium hydroxide monohydrate (3.544 g, 84.453 mmol, 2.00 equiv.) was added. The mixture, which turned into a dark reddish-brown solution, was stirred vigorously (1000 rpm) for 1 hour, after which neat chloromethyl ethyl ether (11.8 mL, 126.80 mmol, 3.00 equiv.) was added dropwise rapidly via syringe. After stirring at 0 °C for 2 h, the dark brown solution was diluted with aqueous NaOH (200 mL, 1 N), stirred for 2 min, the THF was removed under reduced pressure, 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, the layers were separated, 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 an amber 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% yield, 2 steps) as a bright yellow oil. NMR indicated the product.

[0081] 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*).

[0082] Example 2: Synthesis of Boropinacolate Intermediate [ka] Prior to use, bromothiophene was azeotropically dried using toluene (4 × 10 mL). In a nitrogen-filled glovebox, 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)Cl (1.276 g, 1.563 mmol, 0.05 equiv.), and B2Pin (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 mantle, slowly cooled to 23 °C, suction filtered through a pad of silica gel, washed with CHCl (4 × 20 mL), and the clear dark gray / black filtrate was concentrated and residual 1,4-dioxane was azeotropically removed using toluene (3 × 10 mL). The black mixture was then suspended in hexane (50 mL), stirred vigorously (1000 rpm) for 20 minutes, suction filtered through Celite, rinsed with hexane (4 × 20 mL), and the resulting pale red-orange filtrate solution was concentrated, diluted with CHCl (10 mL), suction filtered through silica gel, washed with CHCl (4 × 20 mL), and concentrated to give boropinacolate thiophene (8.303 g, 20.745 mmol, 66%, 71% pure by NMR) as a red-orange amorphous oil. NMR showed the product to contain residual B2Pin2 and a protodebrominated by-product.

[0083] 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 C NMR (126 MHz, chloroform-d) δ 159.17, 135.96, 102.29, 94.95, 83.34, 64.16, 24.77, 15.14.

[0084] Example 3: Synthesis of tethered iodophenyl ether intermediates [ka] A white heterogeneous mixture of 2-iodophenol (2.000 g, 9.091 mmol, 2.00 equiv.), K2CO3 (2.513 g, 18.180 mmol, 4.00 equiv.), and 1,4-dibromobutane (0.54 mL, 4.545 mmol, 1.00 equiv.) in acetone (25 mL) under nitrogen and equipped with a reflux condenser was placed in a heated mantle at 60 °C and stirred (500 rpm) for 36 h. After stirring, the white heterogeneous mixture was removed from the mantle. The mixture was extracted, cooled to 23 °C, diluted with CHCl (50 mL), stirred for 2 min, suction filtered through a pad of Celite, rinsed with CHCl (4 × 20 mL), and the resulting pale yellow filtrate was concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatographic purification system with 25% CHCl in hexanes to give the iodophenyl ether (2.024 g, 4.096 mmol, 90%) as a white solid. NMR indicated pure product.

[0085] 1 H NMR (500MHz, chloroform-d) δ 7.77(dd, J=7.8, 1.8Hz, 2H), 7.34-7.22(m, 2H), 6.83(d, J=8.2Hz, 2H), 6.70(t, J=7.6Hz, 2H), 4.14(d, J=5.3Hz, 4H), 2.17-2.06(m, 4H). 13 C NMR (126 MHz, chloroform-d) δ 157.42, 139.39, 129.44, 129.43, 122.42, 112.11, 112.09, 86.68, 68.61, 26.04.

[0086] Example 4: Synthesis of precursors for ligands 1-10 [ka] A mixture of thiophene (1.512 g, 5.321 mmol, 3.00 equiv.), KPO (3.389 g, 15.966 mmol, 9.00 equiv.), Pd(AmPhos)Cl (0.251 g, 0.3548 mmol, 0.20 equiv.), and bisphenyl iodide (0.876 g, 1.774 mmol, 1.00 equiv.) was prepared. The mixture was evacuated and then backfilled with nitrogen. This process was repeated three more times. Then, deoxygenated 1,4-dioxane (18.0 mL) and deoxygenated water (1.8 mL) were added sequentially via syringe. The mixture was sealed with a PTFE cap under a nitrogen purge and placed in a heated mantle at 50 °C. After 36 hours of stirring (1000 rpm), the black mixture was removed from the mantle, slowly cooled to 23 °C, and suction filtered onto a pad of silica gel, washing with CHCl (4 x 20 mL). The clear, dark gray / black filtrate was concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatographic purification system with 25% to 75% CHCl in hexanes to give the bisthiophene (0.712 g, 1.284 mmol, 72%) as a bright yellow foam. NMR indicated pure product.

[0087] 1 H NMR (500MHz, chloroform-d) δ 7.42(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, 2H), 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 C NMR (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.

[0088] Example 5: Synthesis of precursors for ligands 1-10 [ka] The bisthiophene was azeotropically dried using PhMe (4 x 10 mL) prior to use. A clear, colorless solution of thiophene (475.0 mg, 0.8563 mmol, 1.00 equiv.) in deoxygenated anhydrous THF (15 mL) in a nitrogen-filled glovebox was placed in a freezer cooled to -35 °C for 12 hours, after which a pre-cooled solution of n-BuLi (1.00 mL, 2.569 mmol, 3.00 equiv., titrated 2.50 M in hexanes) was added dropwise via syringe. The now bright yellow-orange mixture was left in the freezer for 4 hours, after which it was removed and solid 1,2-dibromotetrachloroethane (837.0 mg, 2.569 mmol, 3.00 equiv.) was rapidly added dropwise with stirring (500 rpm). After stirring at 23 °C for 2 h, the now pale yellow heterogeneous mixture was removed from the glovebox, neutralized with aqueous phosphate buffer (50 mL, pH = 8, 0.05 M), diluted with CHCl (30 mL) and brine (20 mL), poured into a separatory funnel, and the layers were separated. The organics were washed with a saturated aqueous mixture of phosphate buffer (pH = 8, 0.05 M) and brine (2 × 40 mL, 1:1). The remaining organics were combined with the aqueous layer using CHCl (2 × 20 mL), dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography with 25% to 75% CHCl in hexanes to give dibromothiophene as a pale yellow amorphous oil (544.0 mg, 0.7635 mmol, 89%). NMR indicated a pure product.

[0089] 1 H NMR (500MHz, chloroform-d) δ 7.37(dd, J=7.5, 1.7Hz, 2H), 7.28(ddd, J=8.3, 7.4, 1.8Hz, 2H), 7.22(s, 2H), 6.97(td, J=7.5, 1.1Hz, 2H), 6.90(dd, J=8.3, 1.1Hz, 2H), 4.82(s, 4H), 3.97-3.93(m, 4H), 3.48(q, J=7.1Hz, 4H), 1.84-1.80(m, 4H), 1.00(t, J=7.1Hz, 6H). 13C 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.

[0090] Example 6: Synthesis of Ligand 1 [ka] To a vial equipped with a stir bar was added the dibromide (0.200 g, 0.2807 mmol, 1.00 equiv.), K3PO4 (0.715 g, 3.369 mmol, 12.0 equiv.), Pd(AmPhos)Cl2 (40.0 mg, 0.0561 mmol, 0.20 equiv.), and 3,5-di-tert-butylphenylboropinacolate (0.355 g, 1.123 mmol, 4.00 equiv.). The mixture was evacuated and then backfilled with nitrogen. This process was repeated three more times, followed by the sequential addition of deoxygenated 1,4-dioxane (6.0 mL) and water (0.6 mL) via syringe. The vial was sealed with a PTFE cap under a nitrogen purge and then placed in a heated mantle at 50 °C. After 36 hours of stirring (1000 rpm), the purple-black mixture was removed from the mantle, slowly cooled to 23 °C, and suction filtered onto a pad of silica gel, washing with CHCl (4 x 20 mL). The clear purple filtrate was concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatographic purification system with 25% to 100% CHCl in hexanes to give the bis-protected coupled 3,5-di-tert-butylphenylthiophene (0.223 g, 0.2394 mmol, 85%) as a white foam. NMR indicated pure product.

[0091] To a solution of the protected bis(hydroxythiophene) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL). The dark amber solution was vigorously stirred (1000 rpm) under nitrogen for 24 h at 23 °C, then diluted with aqueous HCl (25 mL, 1N) and aqueous CHCl (20 mL). The biphasic mixture was poured into a separatory funnel, the layers separated, the organics washed with aqueous HCl (2 x 20 mL, 1N), the residual organics extracted from the aqueous layer using CHCl (2 x 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatographic purification system with 25% to 100% CHCl in hexanes to give the bis(hydroxythiophene) ligand (98.5 mg, 0.1208 mmol, 51%, 43% 2 steps) as a white amorphous foam. NMR indicated a pure product.

[0092] 1 H NMR (500MHz, chloroform-d) δ 7.68(d, J=1.7Hz, 4H), 7.43(dd, J=7.6, 1.7Hz, 2H), 7.34(t, J=1.8Hz, 2H), 7.28(ddd, J=8.2, 7.4, 1.7Hz, 2H), 7.10-7. 06(m, 2H), 7.06(s, 2H), 6.96(s, 2H), 6.89(dd, J=8.3, 1.2Hz, 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.

[0093] Characterization of protected ligand 1: 1H NMR (500MHz, chloroform-d) δ 7.61 (d. dd. 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.

[0094] Example 7: Synthesis of Procatalyst 1 [ka] Ligand 1 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (3.3 mg, 0.00711 mmol, 1.00 equiv.) in C6D6 (0.14 mL) was added dropwise to a solution of thiophene (5.8 mg, 0.00711 mmol, 1.00 equiv.) in anhydrous C6D6 (1.28 mL). After stirring (500 rpm) for 45 min, the bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to yield the zirconium complex as a 0.005 M solution in C6D6. The same procedure using PhMe can be used to prepare the procatalyst solution used immediately after filtration in polymerization experiments.

[0095] 1H NMR (500MHz, benzene-d6) δ 7.78(d, J=1.8Hz, 4H), 7.56(t, J=1.8Hz, 2H), 7.20-7.17(m, 2H), 7.12-7.11(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.

[0096] Example 8: Synthesis of Procatalyst 2 [ka] Ligand 1 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn (4.5 mg, 0.00822 mmol, 1.00 equiv.) in C6D6 (0.18 mL) was added dropwise to a solution of thiophene (6.7 mg, 0.00822 mmol, 1.00 equiv.) in anhydrous C6D6 (1.48 mL). After stirring (500 rpm) for 45 min, the bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to yield the hafnium complex as a 0.005 M solution in C6D6. The same procedure using PhMe can be used to prepare the procatalyst solution used immediately after filtration in polymerization experiments.

[0097] 1H NMR (500MHz, ベンゼン-d6) δ 7.75(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, 0.7H z, 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), 5.9 2(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=12.7H z, 2H), 1.45 (d, J=12.8Hz, 3H), 1.33 (s, 40H), 0.78 (t, J=9.6Hz, 2H), 0.41 (d, J=11.4Hz, 2H). 13 C NMR (126MHz, ベンゼン-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.

[0098] Example 9: Synthesis of Coordinator 2

change

[0099] To a solution of the protected coupled bisthiophene (101.0 mg, 0.0893 mmol, 1.00 equiv) in CH2Cl2 (5 mL) and 1,4-dioxane (5 mL) under nitrogen was added concentrated HCl (3 mL, 37% aqueous solution) via syringe. The bright yellow solution was stirred (500 rpm) for 16 h, diluted with aqueous HCl (10 mL, 1N) and aqueous CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with aqueous HCl (1 x 10 mL, 1N). The remaining organics were extracted from the aqueous solution using CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography with 10% to 35% CHCl in hexanes to give bis-hydroxythiophene (90.4 mg, 0.0890 mmol, 99%, 32% in two steps) as a white foam. NMR indicated pure product.

[0100] 1 H NMR (500MHz, クロロホルム-d) δ 8.45(s, 2H), 7.98(d, J=8.9Hz, 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, 2.0Hz, 2H), 7.44(d, J=3.6Hz, 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 (126MHz, クロロホルム-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, 125.29, 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.

[0101] Evaluation of the characteristics of the protective seat: 1 H NMR (500MHz, クロロホルム-d) δ 8.44(s, 2H), 8.04-7.96(m, 4H), 7.97-7.88(m, 4H), 7.64(dd, J=7.6, 1.8Hz, 2H), 7.59( s, 2H), 7.57 (ddd, J=8.9, 6.4, 2.1Hz, 4H), 7.30 (td, J=7.8, 1.8Hz, 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.

[0102] Example 10: Synthesis of Ligand 3 [ka] The dibromide was azeotropically dried using PhMe (4 × 10 mL) prior to use. A solid mixture of dibromide (0.850 g, 1.193 mmol, 1.00 equiv.), carbazole (1.667 g, 5.965 mmol, 5.00 equiv.), CuO (0.854 g, 5.965 mmol, 5.00 equiv.), and KCO (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 refilled with nitrogen. This process was repeated four more times, after which deoxygenated anhydrous xylene (20.0 mL) was added, followed by neat N,N'-dimethylethylenediamine (1.30 mL, 11.930 mmol, 10.00 equiv.) via syringe. After 72 hours of vigorous stirring (1000 rpm), the dark red heterogeneous mixture was removed from the mantle, slowly cooled to 23 °C, diluted with CHCl (30 mL), vigorously stirred (1000 rpm) for 2 minutes, and vacuum filtered onto silica gel using CHCl as eluent, rinsing with CHCl (4 × 25 mL). The bright orange filtrate was concentrated onto Celite and purified by silica gel chromatography with 45% CHCl in hexanes to give biscarbazoyl-thiophene (0.317 g, 0.2857 mmol, 24%) as a bright yellow foam. NMR indicated the product contained minor impurities. This product was used in subsequent reactions without further purification.

[0103] To a solution of the 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) under nitrogen at 23 °C. After 16 h of vigorous stirring (1000 rpm), the pale amber solution was diluted with aqueous HCl (20 mL, 1 N) and aqueous CHCl (20 mL), poured into a separatory funnel, and the layers were separated. The organics were washed with aqueous HCl (2 x 20 mL). The remaining organics were extracted from the aqueous layer using CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography with 10% to 30% CHCl in hexanes to give the hydroxythiophene (0.252 g, 0.2537 mmol, 89%, 21% yield, 2 steps) as a bright yellow foam. NMR showed a pure product.

[0104] 1 H NMR (500MHz, chloroform-d) δ 8.10(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=8.5Hz, 4H), 7. 18(s, 2H), 7.12(td, J=7.5, 1.1Hz, 2H), 6.91(dd, J=8.3, 1.1Hz, 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.

[0105] Characterization of protected ligand 3: 1H NMR (500MHz, chloroform-d) δ 8.10(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.

[0106] Example 11: Synthesis of Procatalyst 5 [ka] Ligand 3 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (7.2 mg, 0.0157 mmol, 1.00 equiv.) in C6D6 (0.30 mL) was added dropwise to a clear, colorless solution of thiophene (15.6 mg, 0.0157 mmol, 1.00 equiv.) in anhydrous C6D6 (1.25 mL). After stirring (500 rpm) for 1 h, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.01 M solution in C6D6. NMR analysis indicated the product was stable. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M) to be used immediately after filtration in polymerization experiments.

[0107] 1H NMR (400MHz, ベンゼン-d6) δ 8.42(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, 1.9Hz, 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 (101MHz, ベンゼン-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.

[0108] Example 12: Synthesis of プロcatalyst 6

change

[0109] 1 H NMR (400MHz, benzene-d6) δ 8.44(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). 13C 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, 126.04, 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.

[0110] Example 13: Synthesis of Ligand 4 [ka] A mixture of the dibromide (361.5 mg, 0.5074 mmol, 1.00 equiv), Pd(AmPhos)Cl (72.0 mg, 0.1015 mmol, 0.20 equiv), KPO (969.0 mg, 4.566 mmol, 9.00 equiv), and m-terphenylboropinacolate ester (542.0 mg, 1.522 mmol, 3.00 equiv) was evacuated and backfilled with nitrogen, and this process was repeated four more times, followed by the sequential addition of freshly sparged deoxygenated 1,4-dioxane (6.0 mL) and HO (0.8 mL). The golden-brown mixture was then placed in a heated mantle at 50 °C and stirred vigorously (1000 rpm) for 48 h. The dark gray mixture was removed from the mantle, cooled to ambient temperature, diluted with CHCl (20 mL), suction filtered through a pad of silica gel, and rinsed with CHCl (4 x 20 mL). The resulting filtrate was concentrated onto Celite and purified by silica gel chromatography from 10% CHCl to 65% CHCl in hexanes to give the protected coupling product (393.0 mg, 0.3886 mmol, 77%) as a white foam. NMR indicated the product contained traces of impurities.

[0111] To a solution of the protected linked bisthiophene (393.0 mg, 0.3886 mmol, 1.00 equiv) in CH2Cl2 (5 mL) and 1,4-dioxane (5 mL) under nitrogen was added concentrated HCl (5 mL, 37% aqueous solution) via syringe. The bright yellow solution was stirred (500 rpm) for 20 h, diluted with aqueous HCl (10 mL, 1N) and aqueous CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with aqueous HCl (1 x 10 mL, 1N). The remaining organics were extracted from the aqueous solution using CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography with 25% to 55% CHCl in hexanes to give bis-hydroxythiophene (213.0 mg, 0.2380 mmol, 61%, 47% yield, 2 steps) as a white foam. NMR indicated pure product.

[0112] 1 H NMR (500MHz, chloroform-d) δ 8.15(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.

[0113] Characterization of protected ligand 4: 1H NMR (500MHz, chloroform-d) δ 7.98(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.

[0114] Example 14: Synthesis of Procatalyst 7 [ka] Ligand 4 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (4.7 mg, 0.0104 mmol, 1.00 equiv.) in C6D6 (0.19 mL) was added dropwise to a clear, colorless solution of thiophene (9.3 mg, 0.0104 mmol, 1.00 equiv.) in anhydrous C6D6 (1.05 mL). After stirring (500 rpm) for 1 h, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.01 M solution in C6D6. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M), which is used immediately after filtration in polymerization experiments.

[0115] 1H NMR (400MHz, benzene-d6) δ 8.38(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.

[0116] Example 15: Synthesis of Procatalyst 8 [ka] Ligand 4 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (6.3 mg, 0.0115 mmol, 1.00 equiv.) in C6D6 (0.27 mL) was added dropwise to a solution of thiophene (10.3 mg, 0.0115 mmol, 1.00 equiv.) in anhydrous C6D6 (1.00 mL). After stirring (500 rpm) for 1 h, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.01 M solution in C6D6. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M), which is used immediately after filtration in polymerization experiments.

[0117] 1 H NMR (400MHz, benzene-d6) δ 8.36(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.

[0118] Example 16: Synthesis of Boropinacolate Intermediate for Ligand 4 [ka] A mixture of 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.) in anhydrous, deoxygenated 1,4-dioxane (100 mL) in a nitrogen-filled glovebox was heated to 100 °C in a mantle. The mixture was placed in a jar and stirred vigorously (1000 rpm) for 24 hours, removed from the heating mantle, slowly cooled to 23 °C, and suction filtered through a pad of silica gel, rinsing with CHCl (4 x 25 mL). The resulting filtrate solution was concentrated onto Celite and purified by silica gel chromatography from 10% CHCl to 100% CHCl in hexanes to give the boropinacolate ester (3.446 g, 9.672 mmol, 89%) as a white solid. NMR indicated pure product.

[0119] 1 H NMR (500MHz, chloroform-d) δ 8.08(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.

[0120] Example 17: Synthesis of Ligand 5 [ka] A mixture of the dibromide (268.7 mg, 0.3771 mmol, 1.00 equiv), Pd(AmPhos)Cl (53.0 mg, 0.0754 mmol, 0.20 equiv), KPO (720.0 mg, 3.394 mmol, 9.00 equiv), and m-bis(3,5-di-t-butylphenyl)terphenylboropinacolate ester (689.0 mg, 1.186 mmol, 3.15 equiv) was evacuated and backfilled with nitrogen, and this process was repeated four more times, followed by the sequential addition of freshly sparged deoxygenated 1,4-dioxane (7.5 mL) and HO (1.0 mL). The golden-brown mixture was then placed in a heated mantle at 50 °C and stirred vigorously (1000 rpm) for 48 h. The dark gray mixture was removed from the mantle, cooled to ambient temperature, diluted with CHCl (20 mL), suction filtered through a pad of silica gel, and rinsed with CHCl (4 x 20 mL). The resulting filtrate was concentrated onto Celite and purified by silica gel chromatography from 10% CHCl to 50% CHCl in hexanes to give the protected coupled product (476.0 mg, 0.3260 mmol, 86%) as a white foam. NMR indicated a pure product.

[0121] To a solution of the protected bis-hydroxythiophene (476.0 mg, 0.3260 mmol, 1.00 equiv.) in CHCl (5 mL) and 1,4-dioxane (5 mL) under nitrogen, concentrated HCl (5 mL, 37% aqueous solution) was added via syringe. The bright yellow solution was stirred (500 rpm) for 24 h, diluted with aqueous HCl (10 mL, 1 N) and aqueous CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with aqueous HCl (1 x 10 mL, 1 N). The remaining organics were extracted from the aqueous solution using CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography with 10% to 25% CHCl in hexanes to give the bis-hydroxythiophene (251.0 mg, 0.1868 mmol, 57%) as a white foam. NMR showed a pure product.

[0122] 1H NMR (400MHz, クロロホルム-d) δ 8.02 (d, J=1.6Hz, 4H), 7.65 (t, J=1.7Hz, 2H), 7.52 (s, 4H), 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 (101MHz, クロロホルム-d) δ 153.95, 151.14, 148.35, 143.27, 141.04, 134.49, 132.94, 131.67, 129.45, 125.13, 124.8 7. 124.72, 122.79, 122.01, 121.52, 120.04, 119.60, 113.86, 69.68, 35.01, 31.55, 25.79.

[0123] Characteristics evaluation of Protector's Matching Seat 5: 1 H NMR (400MHz, クロロホルム-d) δ 7.94 (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, 2 H), 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).

[0124] 13C 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.

[0125] Example 18: Synthesis of procatalyst 9 [ka] Ligand 5 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (5.9 mg, 0.01302 mmol, 1.00 equiv.) in C6D6 (0.24 mL) was added dropwise to a clear, colorless solution of thiophene (17.5 mg, 0.01302 mmol, 1.00 equiv.) in anhydrous C6D6 (1.00 mL). After stirring (500 rpm) for 1 h, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to yield the zirconium complex as a 0.01 M solution in C6D6. The same procedure using PhMe can be used to prepare a procatalyst solution (0.005 M) to be used immediately after filtration in polymerization experiments.

[0126] 1H NMR (400MHz, ベンゼン-d6) δ 8.44 (d, J=1.6Hz, 4H), 8.04 (t, J=1.7Hz, 2H), 7.68 (d, J=1.8Hz, 8H), 7.45 (t, J=1.8Hz, 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=1 2.3Hz, 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 (101MHz, ベンゼン-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.

[0127] Example 19: Synthesis of プロcatalyst 10

change

[0128] 1 H NMR (400MHz, benzene-d6) δ 8.42(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.

[0129] Example 20: Synthesis of Boropinacolate Ester Intermediate for Ligand 5 [ka] In a nitrogen-filled glovebox at −35°C (pre-cooled for 16 h), a pre-cooled solution of t-BuLi (3.6 mL, 6.122 mmol, 3.30 equiv., 1.7 M in pentane) in anhydrous, deoxygenated pentane (20 mL) was added dropwise over 10 min to a pre-cooled solution of 3,5-bis-(3,5-di-t-buphenyl)-m-terphenyl bromide (0.990 g, 1.855 mmol, 1.00 equiv.) in pentane / EtO (20 mL, 1:1). At this point, the bright yellow mixture was placed in a freezer (−35°C) for 4 h, after which neat i-PrOBPin (1.25 mL, 6.122 mmol, 3.30 equiv.) was added via syringe. At this point, the pale yellow heterogeneous mixture was stirred at 23 °C for 3 h, i-PrOH (3 mL) was added, the mixture was removed from the glovebox, water (20 mL) and EtO (30 mL) were added, the biphasic mixture was stirred for 2 min, poured into a separatory funnel, the layers were separated, the organics were washed with water (2 × 25 mL), the remaining organics were extracted with EtO (2 × 25 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography on an ISCO with hexane-50% CHCl in hexane to give mesityl-m-terphenylboropinacolate ester (0.689 g, 1.187 mmol, 64%) as a white foam. NMR indicated pure product.

[0130] 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.

[0131] Example 21: Ligand 5-mediated synthesis of bromide intermediate [ka] A mixture of tribromobenzene (2.299 g, 7.303 mmol, 1.00 equiv.), 3,5-di-t-butylphenylboropinacolate ester (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 back-filled with nitrogen. This evacuation / back-filling process was repeated three more times, followed by addition of freshly deoxygenated THF (50 mL) and HO (5 mL). 0.0 mL) were added simultaneously via syringe, and the bright yellow mixture was placed in a heated mantle at 70 °C and stirred vigorously (1000 rpm) for 24 h, removed from the mantle, slowly cooled to 23 °C, and the bright yellow suspension was suction filtered through silica gel, rinsed with CHCl (4 × 20 mL). The yellow filtrate solution was concentrated onto Celite and purified by silica gel chromatography with hexane to give 3,5-bis-(3,5-di-t-buphenyl)phenyl bromide (0.990 g, 1.855 mmol, 25%) as a white solid. NMR indicated pure product.

[0132] 1 H NMR (500MHz, chloroform-d) δ 7.72-7.69(m, 3H), 7.52(t, J=1.8Hz, 2H), 7.44(d, J=1.8Hz, 4H), 1.42(s, 38H). 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.

[0133] Example 22: Synthesis of Ligand 6 [ka] To a vial equipped with a stir bar was added the dibromide (0.407 g, 0.5712 mmol, 1.00 equiv.), K3PO4 (1.091 g, 5.141 mmol, 9.0 equiv.), Pd(AmPhos)Cl2 (81.0 mg, 0.1142 mmol, 0.20 equiv.), and anthracenylboropinacol ester (0.960 g, 1.588 mmol, 2.78 equiv.). The mixture was evacuated and then backfilled with nitrogen. This process was repeated three more times, followed by the sequential addition of deoxygenated 1,4-dioxane (6.0 mL) and water (0.6 mL) via syringe. The vial was sealed with a PTFE cap under a nitrogen purge and then placed in a heated mantle at 50 °C. After 36 h of stirring (1000 rpm), the purple-black mixture was removed from the mantle and gradually cooled to 23 °C. It was then vacuum filtered over a pad of silica gel, washed with CHCl (4 x 20 mL), and the clear purple filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed on a rotary evaporator with toluene (3 x 10 mL). The resulting black mixture was suspended in CHCl (10 mL) and vacuum filtered through silica gel to remove residual insoluble impurities. It was then washed with CHCl (4 x 20 mL). The purple filtrate was concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatographic purification system with 25% to 65% CHCl in hexanes to afford the bis-protected linked thiophene (0.588 g, 0.3899 mmol, 68%) as a bright yellow foam. NMR indicated a pure product.

[0134] To a solution of the protected bis(hydroxythiophene) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL). The dark amber solution was vigorously stirred (1000 rpm) under nitrogen for 24 h at 23 °C, then diluted with aqueous HCl (25 mL, 1N) and aqueous CHCl (20 mL). The biphasic mixture was poured into a separatory funnel, the layers separated, the organics washed with aqueous HCl (2 x 20 mL, 1N), the residual organics extracted from the aqueous layer using CHCl (2 x 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatographic purification system with 25% to 80% CHCl in hexane to give the bis(hydroxythiophene) ligand (0.373 g, 0.2680 mmol, 69%, 47% 2 steps) as a bright yellow amorphous foam. NMR indicated a pure product.

[0135] 1 H NMR (500MHz, chloroform-d) δ 8.02(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(t d, 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.

[0136] Characterization of the protected ligand: 1 H NMR (400MHz, chloroform-d) δ 8.02(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, 2 H), 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, 2 H), 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). 13 C 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.

[0137] Example 23: Synthesis of procatalyst 11 [ka] Ligand 6 was azeotropically dried using PhMe (4 × 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn (7.1 mg, 0.0157 mmol, 1.00 equiv) in toluene (0.29 mL) was added dropwise to a clear, bright yellow solution of thiophene (21.8 mg, 0.0157 mmol, 1.00 equiv) in anhydrous toluene (2.80 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was concentrated, and the resulting bright yellow 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), vigorously stirred (1000 rpm) for 2 min, filtered through a 0.20 μm PTFE filter, rinsed with hexane (3 × 3 mL), and the hexane filtrate was concentrated to give the zirconium complex (25.7 mg, 0.0154 mmol, 98%) as a bright yellow solid. NMR indicated the product was a 2.2:1 mixture of rotamers.

[0138] 1 H NMR (400MHz, benzene-d6) δ 8.72-8.67(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, 18H), 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). 13C 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, 126.1 0, 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, 34.67, 34.63, 31.42, 31.29, 30.75, 30.60, 25.72.

[0139] Example 24: Synthesis of procatalyst 12 [ka] Ligand 6 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (6.1 mg, 0.0112 mmol, 1.00 equiv.) in C6D6 (0.25 mL) was added dropwise to a clear, bright yellow solution of thiophene (15.6 mg, 0.0112 mmol, 1.00 equiv.) in anhydrous C6D6 (1.00 mL). After stirring (500 rpm) for 20 min, the pale yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.009 M solution in C6D6. NMR indicated the product. The same procedure using PhMe can be used to prepare a procatalyst solution (0.005 M) to be used immediately after filtration in polymerization experiments.

[0140] 1H NMR (400MHz, ベンゼン-d6) δ 8.68 (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, 2H), 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). 13 C NMR (101MHz, ベンゼン-d6) δ 156.08, 155.66, 150.85, 150.41, 147.82, 147.64, 146.26, 139.12, 138.79, 133.13 ,131.61,131.32,130.62,130.13,129.42,129.39,128.89,128.13,127.97,127.0 3, 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.

[0141] Example 25: Synthesis of Coordinator 6 Tetrafluoroethylene Intermediate

change

[0142] 1 H NMR (500MHz, chloroform-d) δ 8.49(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). 13C 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.

[0143] Example 26: Synthesis of the bromide intermediate for ligand 6 [ka] To a pale yellow solution of di-t-butylanthracene (0.791 g, 1.653 mmol, 1.00 equiv.) in CHCl / MeCN (40 mL, 1:1) at 23 °C, solid dibromodimethylhydantoin (0.250 g, 0.8761 mmol, 0.53 equiv.) was added all at once. The bright yellow suspension was stirred (500 rpm) for 4 h, after which TLC showed complete conversion of the starting anthracene. The solution was concentrated onto Celite and purified by silica gel chromatography with hexane to give bromoanthracene (0.912 g, 1.635 mmol, 99%) as a white foam. NMR showed pure product.

[0144] 1 H NMR (400MHz, chloroform-d) δ 8.58(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.

[0145] Example 27: Synthesis of an anthracenyl intermediate for ligand 6 [ka] A mixture of bromoanthracene (0.623 g, 1.687 mmol, 1.00 equiv.), Pd(AmPhos)Cl (0.119 g, 0.1687 mmol, 0.10 equiv.), KPO (1.611 g, 7.590 mmol, 4.50 equiv.), and boropinacolate ester (0.800 g, 2.530 mmol, 1.50 equiv.) was evacuated and then back-filled with nitrogen four more times, followed by the addition of freshly sparged deoxygenated 1,4-dioxane (15 mL) and water (1.5 mL). The brown mixture was placed in a heating mantle at 50 °C and stirred for 6 h, after which TLC indicated complete consumption of the starting bromoanthracene, at which point the purple-black mixture was diluted with CHCl (20 mL) and suction filtered through a pad of silica gel, rinsing with CHCl (4 × 20 mL). The filtrate was concentrated onto Celite and purified by silica gel chromatography with hexane to give 3,5-di-t-butylphenyl-bis-t-butylanthracene (0.791 g, 1.653 mmol, 98%) as a white foam. NMR indicated pure product.

[0146] 1 H NMR (400MHz, chloroform-d) δ 8.40(s, 1H), 8.00(dd, J=8.9, 0.6Hz, 2H), 7.77(dt, J=1.8, 0.8Hz, 2H), 7.60-7.56(m, 3H), 7.38(d, J=1.8Hz, 2H), 1.46(s, 18H), 1.36(s, 18H). 13 C NMR (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.

[0147] Example 28: Synthesis of bromoanthracene intermediate for ligand 6 [ka] To a pale yellow, slight suspension of di-t-butylanthracene (1.035 g, 3.563 mmol, 1.00 equiv.) in CHCl / MeCN (50 mL, 1:1) at 23 °C was added solid dibromodimethylhydantoin (0.510 g, 1.782 mmol, 0.50 equiv.) all at once. At this point, the dark bright yellow suspension was stirred (500 rpm) for 90 min, after which the mixture was concentrated, suspended in MeOH (30 mL), placed in a heated mantle at 70 °C, and vigorously stirred (1000 rpm) for 30 min. The bright yellow mixture was then slowly and gradually cooled to 23 °C, suction filtered, and the resulting solid was washed with MeOH (4 × 10 mL) and dried under reduced pressure to give bromo-di-t-butylanthracene (0.623 g, 1.687 mmol, 47%) as an off-white powder. NMR indicated pure product.

[0148] 1 H NMR (400MHz, chloroform-d) δ 8.40(dt, J=1.6, 0.7Hz, 2H), 8.31(s, 1H), 7.90(dt, J=8.9, 0.6Hz, 2H), 7.56(dd, J=8.8, 1.8Hz, 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.

[0149] Example 29: Synthesis of Ligand 7 [ka] To a vial equipped with a stir bar was added the dibromide (0.386 g, 0.5418 mmol, 1.00 equiv.), KPO (1.035 g, 4.876 mmol, 9.0 equiv.), Pd(AmPhos)Cl (78.0 mg, 0.1084 mmol, 0.20 equiv.), and mesityl terphenylboropinacol ester (0.716 g, 1.625 mmol, 3.00 equiv.). The mixture was evacuated and then backfilled with nitrogen. This process was repeated three more times, followed by the sequential addition of deoxygenated 1,4-dioxane (6.0 mL) and water (0.6 mL) via syringe. The vial was sealed with a PTFE cap under a nitrogen purge and then placed in a heated mantle at 50 °C. After 36 h of stirring (1000 rpm), the purple-black mixture was removed from the mantle and gradually cooled to 23 °C. It was then vacuum filtered over a pad of silica gel, washed with CHCl (4 x 20 mL), and the clear purple filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed on a rotary evaporator with toluene (3 x 10 mL). The resulting black mixture was suspended in CHCl (10 mL) and vacuum filtered through silica gel to remove residual insoluble impurities. It was then washed with CHCl (4 x 20 mL). The purple filtrate was concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatographic purification system with 25% to 65% CHCl in hexanes to afford the bis-protected linked thiophene (0.519 g, 0.4400 mmol, 81%) as a white foam. NMR indicated a pure product.

[0150] To a solution of the protected bis(hydroxythiophene) in CHCl (5 mL) and 1,4-dioxane (5 mL) was added concentrated HCl (5 mL). The dark amber solution was vigorously stirred (1000 rpm) under nitrogen for 24 h at 23 °C, then diluted with aqueous HCl (25 mL, 1N) and aqueous CHCl (20 mL). The biphasic mixture was poured into a separatory funnel, the layers separated, the organics washed with aqueous HCl (2 x 20 mL, 1N), the residual organics extracted from the aqueous layer using CHCl (2 x 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatographic purification system with 25% to 80% CHCl in hexanes to give the bis(hydroxythiophene) ligand (0.324 g, 0.3047 mmol, 69%, 56% 2 steps) as a white foam. NMR indicated a pure product.

[0151] 1 H NMR (500MHz, chloroform-d) δ 7.65(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.

[0152] Characterization of the protected ligand: 1H NMR (400MHz, chloroform-d) δ 7.51(d, J=1.6Hz, 4H), 7.41(dd, J=7.6, 1.8Hz, 2H), 7.24-7.18(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.

[0153] Example 30: Synthesis of procatalyst 13 [ka] Ligand 7 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (7.8 mg, 0.0171 mmol, 1.00 equiv.) in C6D6 (0.32 mL) was added dropwise to a white suspension of thiophene (18.2 mg, 0.0171 mmol, 1.00 equiv.) in anhydrous C6D6 (1.48 mL). After stirring (500 rpm) for 1 h, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to yield the zirconium complex as a 0.01 M solution in C6D6. NMR indicated the product was azeotropically dried using the same procedure with PhMe to prepare a 0.005 M procatalyst solution, which was used immediately after filtration in polymerization experiments.

[0154] 1H NMR (400MHz, ベンゼン-d6) δ 8.17(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, 1 2H), 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 (101MHz, ベンゼン-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.

[0155] Example 31: Synthesis of Hirocatalyst 14

change

[0156] 1 H NMR (400MHz, benzene-d6) δ 8.14(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, 13H), 2.12(s, 14H) ), 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.

[0157] Example 32: Synthesis of mesityl m-terphenyl bromide intermediate for ligand 7 [ka] In a nitrogen-filled glovebox at 23 °C, a solution of 2,4,6-trimethylphenylmagnesium bromide (8.0 mL, 7.943 mmol, 2.50 equiv, 1.0 M in THF) was rapidly added dropwise to a solution of tribromobenzene (1.000 g, 3.177 mmol, 1.00 equiv) and Pd(PPh) (0.367 g, 0.3177 mmol, 0.10 equiv) in anhydrous, deoxygenated THF (30 mL). The resulting reddish-black solution was placed in a heated mantle at 70 °C and stirred vigorously (1000 rpm) for 18 h, removed from the mantle, slowly cooled to 23 °C, neutralized with i-PrOH (5 mL), removed from the glovebox, concentrated, and the resulting dark reddish-black mixture was suspended in CHCl (25 mL), suction filtered over a pad of silica gel, and rinsed with CHCl (4 × 25 mL). The resulting amber solution was concentrated onto Celite and purified by silica gel chromatography with hexane to give 3,5-bis-(2,4,6-trimethylphenyl)-phenylbromide (0.428 g, 1.088 mmol, 34%) as a white solid. NMR indicated pure product.

[0158] 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.

[0159] Example 33: Synthesis of Boropinacolate Intermediate for Ligand 7 [ka] In a nitrogen-filled glovebox at −35°C (pre-cooled for 16 h), a pre-cooled suspension of mesityl-m-terphenyl bromide (2.019 g, 5.133 mmol, 1.00 equiv.) in pentane / EtO (30 mL, 1:1) was added dropwise over 10 min to a pre-cooled solution of t-BuLi (10.0 mL, 16.938 mmol, 3.30 equiv., 1.7 M in pentane) in anhydrous, deoxygenated pentane (45 mL). At this point, the bright yellow mixture was placed in a freezer (−35°C) for 4 h, after which neat i-PrOBPin (3.50 mL, 16.938 mmol, 3.30 equiv.) was added via syringe. At this point, the pale yellow heterogeneous mixture was stirred at 23 °C for 3 h, i-PrOH (3 mL) was added, the mixture was removed from the glovebox, water (20 mL) and EtO (30 mL) were added, the biphasic mixture was stirred for 2 min, poured into a separatory funnel, the layers were separated, the organics were washed with water (2 × 25 mL), the remaining organics were extracted with EtO (2 × 25 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography on an ISCO with hexane-50% CHCl in hexane to give mesityl-m-terphenylboropinacolate ester (2.095 g, 4.757 mmol, 93%) as a white foam. NMR indicated pure product.

[0160] 1 H NMR (500MHz, chloroform-d) δ 7.58(dt, J=2.9, 1.7Hz, 2H), 7.07(p, J=1.8Hz, 1H), 6.94(d, J=2.0Hz, 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.

[0161] Example 34: Synthesis of Ligand 8 [ka] To a vial equipped with a stir bar was added the dibromide (0.390 g, 0.5476 mmol, 1.00 equiv.), KPO (1.046 g, 4.928 mmol, 9.0 equiv.), Pd(AmPhos)Cl (78.0 mg, 0.1095 mmol, 0.20 equiv.), and TRIP-m-terphenylboropinacol ester (1.000 g, 1.643 mmol, 3.00 equiv.). The mixture was evacuated and then backfilled with nitrogen. This process was repeated three more times, followed by the sequential addition of deoxygenated 1,4-dioxane (10.0 mL) and water (1.0 mL) via syringe. The mixture was placed under a nitrogen purge and then placed in a heated mantle at 50 °C. After 48 h of stirring (1000 rpm), the purple-black mixture was removed from the mantle, gradually cooled to 23 °C, diluted with CHCl (20 mL), suction filtered over a silica gel pad, washed with CHCl (4 x 20 mL), and the clear purple filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed on a rotary evaporator with toluene (3 x 10 mL). The resulting black mixture was suspended in CHCl (10 mL), suction filtered through silica gel to remove residual insoluble impurities, washed with CHCl (4 x 20 mL), and the purple filtrate was concentrated onto Celite. The mixture was purified by silica gel chromatography using an ISCO chromatographic purification system with 10% to 60% CHCl in hexanes to afford the bis-protected linked thiophene (0.748 g, 0.4928 mmol, 90%) as a bright yellow foam. NMR indicated a pure product.

[0162] To a solution of the protected bis(hydroxythiophene) in CHCl (10 mL) and 1,4-dioxane (10 mL) was added concentrated HCl (10 mL). The dark amber solution was vigorously stirred (1000 rpm) under nitrogen for 24 h at 23 °C, then diluted with aqueous HCl (25 mL, 1N) and aqueous CHCl (20 mL). The biphasic mixture was poured into a separatory funnel, the layers separated, the organics washed with aqueous HCl (1 x 20 mL, 1N), the residual organics extracted from the aqueous layer using CHCl (2 x 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography using an ISCO chromatographic purification system with 10% to 60% CHCl in hexane to give the bis(hydroxythiophene) ligand (0.610 g, 0.4357 mmol, 88%, 80% yield, 2 steps) as a bright yellow amorphous foam. NMR showed a pure product.

[0163] 1 H NMR (400MHz, chloroform-d) δ 7.76(t, J=1.5Hz, 4H), 7.37(dt, J=7.6, 1.5Hz, 2H), 7.28-7.22(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=6.9Hz, 24H), 1.15(d, J=6.9Hz, 24H), 1.06(d, J=6.9Hz, 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.

[0164] Characterization of the protected ligand: 1H NMR (400MHz, クロロホルム-d) δ 7.61 (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, 5H), 2.81(p, J=6.8Hz, 9H), 1.85(q, J=3.1Hz , 4H), 1.30 (d, J=7.0Hz, 28H), 1.16 (d, J=6.8Hz, 25H), 1.07 (d, J=6.8Hz, 27H), 0.75 (t, J=7.0Hz, 6H). 13 C NMR (101MHz, クロロホルム-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, 12 4.42, 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.

[0165] Example 35: Synthesis of プロcatalyst 15

change

[0166] 1 H NMR (400MHz, benzene-d6) δ 8.28 (d. 7(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=7.1Hz, 12H), 1.09(d, J=6.8Hz, 6H), 0.79(t, J=10.1Hz, 2H), 0.30-0.22(m, 2H). 13C 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, 126.01, 126.12 5.95, 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.

[0167] Example 36: Synthesis of procatalyst 16 [ka] Ligand 8 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (7.0 mg, 0.0129 mmol, 1.00 equiv.) in C6D6 (0.28 mL) was added dropwise to a white suspension of thiophene (18.0 mg, 0.0129 mmol, 1.00 equiv.) in anhydrous C6D6 (1.0 mL). After stirring (500 rpm) for 1 h, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.01 M solution in C6D6. NMR indicated the product existed as a mixture of isomers and rotamers. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M), which is used immediately after filtration in polymerization experiments.

[0168] 1H NMR (400MHz, ベンゼン-d6) δ 8.25(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), 1.32-1.1 2 (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). 13 C NMR (101MHz, ベンゼン-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, 14 1.51, 136.97, 136.57, 135.56, 134.62, 134.32, 133.63, 132.16, 130.18, 129.79, 128.93, 128.59, 128.15, 126.9 8, 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.

[0169] Example 37: Synthesis of odorant intermediate of coordination agent 8

change

[0170] 1 H NMR (500MHz, chloroform-d) δ 7.33(d, J=1.4Hz, 2H), 7.03(s, 4H), 6.95(t, J=1.5Hz, 1H), 2.92(hept, J=6.9Hz, 2H), 2.68( hept, J=6.9Hz, 4H), 1.28(d, J=6.9Hz, 12H), 1.15(d, J=6.8Hz, 12H), 1.04(d, J=6.9Hz, 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.

[0171] Example 38: Synthesis of Boropinacolate Ester Intermediate for Ligand 8 [ka] In a nitrogen-filled glovebox at −35°C (pre-cooled for 16 h), 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) was added dropwise over 10 min to a pre-cooled solution of t-BuLi (10.0 mL, 16.500 mmol, 3.50 equiv, 1.7 M in pentane) in anhydrous, deoxygenated pentane (40 mL). At this point, the bright yellow mixture was placed in a freezer (−35°C) for 4 h, after which neat i-PrOBPin (3.40 mL, 16.500 mmol, 3.50 equiv) was added via syringe. At this point, the pale yellow heterogeneous mixture was stirred at 23 °C for 3 h. i-PrOH (3 mL) was added to neutralize any remaining t-BuLi. The mixture was removed from the glovebox, water (20 mL) and EtO (30 mL) were added, the biphasic mixture was stirred for 2 min, poured into a separatory funnel, the layers separated, the organics washed with water (2 × 25 mL), the remaining organics extracted with EtO (2 × 25 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography on an ISCO with hexane-50% CHCl in hexane to give TRIP-m-terphenylboropinacolate ester (1.165 g, 1.914 mmol, 41%) as a white foam. NMR indicated pure product.

[0172] 1 H NMR (500MHz, chloroform-d) δ 7.61(d, J=1.7Hz, 2H), 7.15(t, J=1.8Hz, 1H), 7.04(s, 4H), 2.94(p, J=6.9Hz, 2H), 2.73(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.

[0173] Example 39: Synthesis of Ligand 9 [ka] The dibromide was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox, a solid mixture of the dibromide (0.864 g, 1.213 mmol, 1.00 equiv.), carbazole (2.043 g, 3.572 mmol, 2.95 equiv.), CuO (0.868 g, 6.063 mmol, 5.00 equiv.), and KCO (3.353 g, 24.260 mmol, 20.0 equiv.) was suspended in anhydrous deoxygenated xylene (25.0 mL) in an oven-dried flask equipped with a stir bar and reflux condenser. Neat N,N'-dimethylethylenediamine (1.30 mL, 11.930 mmol, 10.00 equiv.) was added via syringe. The mixture was then sealed under nitrogen and placed in the glovebox. The mixture was removed from the oven, placed under nitrogen, and placed in a heated mantle at 140 °C with vigorous stirring (1000 rpm) for 72 h. The dark red heterogeneous mixture was removed from the mantle, gradually cooled to 23 °C, diluted with CHCl (30 mL), and vigorously stirred (1000 rpm) for 2 min. It was then vacuum filtered onto silica gel using CHCl as the eluent and rinsed with CHCl (4 x 25 mL). The bright orange filtrate was concentrated onto Celite and purified by silica gel chromatography with 10% to 45% CHCl in hexanes to give biscarbazoyl-thiophene (0.384 g, 0.2269 mmol, 19%) as a white foam. NMR indicated the product contained minor impurities. This product was used in subsequent reactions without further purification.

[0174] To a solution of the 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) under nitrogen at 23 °C. After 16 h of vigorous stirring (1000 rpm), the pale amber solution was diluted with aqueous HCl (20 mL, 1 N) and aqueous CHCl (20 mL), poured into a separatory funnel, and the layers were separated. The organics were washed with aqueous HCl (1 x 20 mL). The remaining organics were extracted from the aqueous layer using CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography with 10% to 50% CHCl in hexanes to give the hydroxythiophene (0.306 g, 0.1941 mmol, 86%, 16% yield, 2 steps) as a pale yellow foam. NMR showed a pure product.

[0175] 1 H NMR (400MHz, chloroform-d) δ 7.91(d, J=1.5Hz, 4H), 7.55(dd, J=7.6, 1.8Hz, 2H), 7.46(d, J=8.3Hz, 4H), 7.28-7 .21(m, 8H), 7.16-7.09(m, 10H), 7.00(s, 2H), 6.95(dd, J=8.3, 1.1Hz, 2H), 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.

[0176] Characterization of protected ligand 9: 1 H NMR (400MHz, クロロホルム-d) δ 7.84(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, 8H), 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 (101MHz, クロロホルム-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, 12 2.69, 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.

[0177] Example 40: Synthesis of Hirocatalyst 17

change

[0178] 1 H NMR (400MHz, benzene-d6) δ 8.09(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, 10 H), 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). 13C 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, 121.1 3, 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.

[0179] Example 41: Synthesis of procatalyst 18 [ka] Ligand 9 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (6.9 mg, 0.0127 mmol, 1.00 equiv.) in C6D6 (0.28 mL) was added dropwise to a clear, colorless solution of thiophene (20.0 mg, 0.0127 mmol, 1.00 equiv.) in anhydrous C6D6 (1.0 mL). After stirring (500 rpm) for 1 h, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.01 M solution in C6D6. NMR indicated the product existed as a mixture of isomers and rotamers. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M), which is used immediately after filtration in polymerization experiments.

[0180] 1H NMR(400MHz、ベンゼン-d6) δ 8.11(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、2 H)、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(d) (d, 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) 13 C NMR(101MHz、ベンゼン-d6) δ 155.15、151.90、148.22、147.82、147.72、147.60、147.09、1 46.58、140.43、140.12、137.87、137.66、133.67、133.24、13 2.70, 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, 3 4.57, 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.

[0181] Example 42: Synthesis of intermediate for ligand 9 [ka] 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 glovebox was added a solution of 2,4,6-triisopropylphenylmagnesium bromide (39.4 mL, 19.693 mmol, 3.30 equiv., 0.5 M in THF) in a dropwise manner. At this point, the bright yellow solution was placed in a heated mantle at 70 °C and stirred (500 rpm) for 48 h. The resulting black solution was removed from the mantle, slowly cooled to 23 °C, neutralized with i-PrOH (10 mL), stirred for 2 min, removed from the glovebox, diluted with CHCl (20 mL), and suction filtered through silica gel, rinsing with CHCl (4 × 20 mL). The filtrate solution was concentrated onto Celite and purified by silica gel chromatography with hexane-25% CHCl in hexane to give the disubstituted carbazole (2.041 g, 3.569 mmol, 58%) as a white solid. NMR indicated pure product.

[0182] 1 H NMR (500MHz, chloroform-d) δ 8.14(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), 2.9 8(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.

[0183] Example 43: Synthesis of Ligand 10 [ka] The dibromide was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox, a solid mixture of the dibromide (0.864 g, 1.213 mmol, 1.00 equiv.), carbazole (1.557 g, 2.863 mmol, 2.36 equiv.), CuO (0.868 g, 6.063 mmol, 5.00 equiv.), and KCO (3.353 g, 24.260 mmol, 20.0 equiv.) was suspended in anhydrous deoxygenated xylene (25.0 mL) in an oven-dried flask equipped with a stir bar and reflux condenser. Neat N,N'-dimethylethylenediamine (1.30 mL, 11.930 mmol, 10.00 equiv.) was added via syringe. The mixture was then sealed under nitrogen and placed in the glovebox. The mixture was removed from the oven, placed under nitrogen, and placed in a heated mantle at 140 °C with vigorous stirring (1000 rpm) for 72 h. The dark red heterogeneous mixture was removed from the mantle, gradually cooled to 23 °C, diluted with CHCl (30 mL), and vigorously stirred (1000 rpm) for 2 min. It was then vacuum filtered onto silica gel using CHCl as eluent and rinsed with CHCl (4 x 25 mL). The bright orange filtrate was concentrated onto Celite and purified by silica gel chromatography with 10% to 50% CHCl in hexanes to give biscarbazoyl-thiophene (0.560 g, 0.3418 mmol, 28%) as a white foam. NMR indicated the product. This product was used in subsequent reactions without further purification.

[0184] To a solution of the 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) under nitrogen at 23 °C. After 16 h of vigorous stirring (1000 rpm), the pale amber solution was diluted with aqueous HCl (20 mL, 1 N) and aqueous CHCl (20 mL), poured into a separatory funnel, and the layers were separated. The organics were washed with aqueous HCl (1 x 20 mL). The remaining organics were extracted from the aqueous layer using CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography with 10% to 50% CHCl in hexanes to give the hydroxythiophene (0.461 g, 0.3029 mmol, 89%, 25% yield, 2 steps) as a pale yellow foam. NMR showed a pure product.

[0185] 1 H NMR (400 MHz, chloroform-d) δ 8.32(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.

[0186] Characterization of protected ligand 10: 1H NMR (400MHz, chloroform-d) δ 8.40(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.

[0187] Example 44: Synthesis of procatalyst 19 [ka] Ligand 10 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (4.5 mg, 0.00979 mmol, 1.00 equiv.) in C6D6 (0.19 mL) was added dropwise to a clear, colorless solution of thiophene (14.9 mg, 0.00979 mmol, 1.00 equiv.) in anhydrous C6D6 (1.75 mL). After stirring (500 rpm) for 1 h, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.005 M solution in C6D6. NMR indicated the product. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M) to be used immediately after filtration in polymerization experiments.

[0188] 1H NMR (400MHz, ベンゼン-d6) δ 8.56 (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 (101MHz, ベンゼン-d6) δ 155.92, 152.28, 151.21, 150.56, 146.08, 142.48, 142.00, 141.42, 141.01, 136.51 ,135.85,133.02,131.32,130.44,128.74,128.15,126.92,125.90,125.55,125.26 123.49, 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.

[0189] Example 45: Synthesis of Hirocatalyst 20

change

[0190] 1 H NMR (400MHz, benzene-d6) δ 8.61-8.55(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), 6.74(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=9.3H) z, 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). 13C NMR (101 MHz, benzene-d6) δ 155.72, 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, 125.62, 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.

[0191] Example 46: Synthesis of intermediates to ligand 11 [ka] A mixture of carbazole (1.062 g, 3.267 mmol, 1.00 equiv.), 3,5-di-t-butylphenylboropinacolate ester (3.100 g, 9.801 mmol, 3.00 equiv.), Pd(PPh3)4 (0.775 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 back-filled with nitrogen; this evacuation / back-filling process was repeated three more times, followed by addition of freshly deoxygenated 1,4-dioxane (30 mL) and HO. (5.0 mL) were added simultaneously via syringe, and the bright yellow mixture was placed in a heated mantle at 100 °C and stirred vigorously (1000 rpm) for 48 h. It was then removed from the mantle and slowly cooled to 23 °C. The bright yellow suspension was suction filtered through silica gel, rinsed with CHCl (4 × 20 mL), and the yellow filtrate solution was concentrated onto Celite and purified by silica gel chromatography with hexane-50% CHCl in hexane to give the disubstituted carbazole (1.551 g, 2.852 mmol, 87%) as a white foam. NMR indicated pure product.

[0192] 1H NMR (500MHz, クロロホルム-d) δ 8.34-8.29 (m, 2H), 8.10 (s, 1H), 7.68 (dd, J=8.4, 1.8Hz, 2H), 7.54 (d, J=1.7Hz, 4H), 7.51 (d, J=8.3Hz, 2H), 7.45 (t, J=1.8Hz, 2H), 1.43 (s, 36H). 13 C NMR (126MHz, クロロホルム-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.

[0193] Example 47: Synthesis of Coordinator 11

change

[0194] To a solution of the 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) under nitrogen at 23 °C. After 16 h of vigorous stirring (1000 rpm), the pale amber solution was diluted with aqueous HCl (20 mL, 1 N) and aqueous CHCl (20 mL), poured into a separatory funnel, and the layers were separated. The organics were washed with aqueous HCl (1 x 20 mL). The remaining organics were extracted from the aqueous layer using CHCl (2 x 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography with 10% to 50% CHCl in hexanes to give the hydroxythiophene (0.461 g, 0.4796 mmol, 77%, 22% yield, 2 steps) as a pale yellow foam. NMR showed a pure product.

[0195] 1 H NMR (500MHz, chloroform-d) δ 8.16(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.

[0196] Characterization of protected ligand 11: 1H NMR (400MHz, chloroform-d) δ 8.11(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.

[0197] Example 48: Synthesis of procatalyst 21 [ka] Ligand 11 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (5.7 mg, 0.0125 mmol, 1.00 equiv.) in C6D6 (0.24 mL) was added dropwise to a clear, colorless solution of thiophene (15.2 mg, 0.0125 mmol, 1.00 equiv.) in anhydrous C6D6 (2.26 mL). After stirring (500 rpm) for 1 h, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.005 M solution in C6D6. NMR analysis indicated the product was stable. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M) to be used immediately after filtration in polymerization experiments.

[0198] 1H NMR (500MHz, ベンゼン-d6) δ 8.52 (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, 18 H), 1.20 (s, 6H), 1.14 (s, 6H), 1.01 (d, J=12.1Hz, 2H), 0.92 (t, J=9.2Hz, 3H), 0.72 (s, 18H), 0.67 (d, J=5.4Hz, 3H), 0.50 (d, J=12.4Hz, 2H). 13 C NMR (126MHz, ベンゼン-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.

[0199] Example 49: Synthesis of プロcatalyst 22

change

[0200] 1 H NMR (500MHz, benzene-d6) δ 8.54(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, 4 H), 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), 6.14-6.10(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), 1.24(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, 122.95, 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.

[0201] Example 50: Synthesis of the dibromide intermediate for ligand 11 [ka] The bisthiophene was azeotropically dried using PhMe (4 x 10 mL) prior to use. A clear, colorless solution of thiophene (1.974 g, 2.534 mmol, 1.00 equiv.) in deoxygenated anhydrous THF (40 mL) in a nitrogen-filled glovebox was placed in a freezer cooled to -35 °C for 20 h, after which a pre-cooled solution of n-BuLi (3.0 mL, 7.601 mmol, 3.00 equiv., titrated 2.50 M in hexanes) was added dropwise via syringe. The amber solution was then removed from the freezer for 3 h, and solid 1,2-dibromotetrachloroethane (2.723 g, 8.361 mmol, 3.30 equiv.) was rapidly added dropwise with stirring (500 rpm). After stirring at 23 °C for 2.5 h, the bright yellow solution was removed from the glovebox, neutralized with brine (50 mL), diluted with CHCl (20 mL) and water (20 mL), poured into a separatory funnel, the layers separated, and the residual organics extracted from the aqueous layer using CHCl (2 × 20 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexane-65% CHCl in hexane to give dibromothiophene (2.054 g, 2.192 mmol, 87%) as a bright yellow amorphous oil. NMR indicated pure product.

[0202] 1 H NMR (400MHz, chloroform-d) δ 7.34(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.

[0203] Example 51: Synthesis of bis-t-octyl-iodophenyl ether intermediate [ka] A white heterogeneous mixture of iodophenol (3.240 g, 9.304 mmol, 2.00 equiv.), KCO (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) under nitrogen and equipped with a reflux condenser was placed in a heated mantle at 60 °C and stirred (500 rpm) for 36 h. After stirring, the white heterogeneous mixture was removed from the mantle. Cool to 23 °C, dilute with CHCl (50 mL), stir for 2 min, suction filter through a pad of Celite, rinse with CHCl (4 × 20 mL), and the resulting pale yellow filtrate was concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatographic purification system with hexane-50% CHCl in hexane to give the iodophenyl ether (3.180 g, 4.426 mmol, 95%) as a white solid. NMR indicated pure product.

[0204] 1 H NMR (500MHz, chloroform-d) δ 7.73(d, J=2.4Hz, 2H), 7.28-7.24(m, 2H), 6.73(d, J=8.6Hz, 2H), 4.14-4 .06(m, 4H), 2.14-2.06(m, 4H), 1.68(s, 4H), 1.32(s, 12H), 0.73(s, 18H). 13 C NMR (126 MHz, chloroform-d) δ 155.12, 144.49, 137.18, 127.03, 111.29, 86.27, 68.68, 56.87, 37.89, 32.35, 31.83, 31.57, 26.11.

[0205] Example 52: Synthesis of 4-t-octyl-2-iodophenol [ka] 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, 1N) in methanol (100 mL) and water (50 mL) under nitrogen was placed in an ice bath and stirred vigorously for 1 h, after which pre-chilled commercial aqueous bleach (26 mL, 20.943 mmol, 1.30 equiv, 5.2% w / w) was added dropwise over 10 min. At this point, the pale, opaque yellow mixture was stirred at 0 °C for 2 h. The mixture was removed from the ice-water bath and stirred at 23 °C for 3 h. Solid NaH2PO4 (20 g) was added, followed by saturated aqueous Na2SO3 (100 mL) to reduce residual iodine and water (100 mL). The mixture was stirred vigorously for 10 min, diluted with CHCl2 (50 mL), and the biphasic yellow mixture was poured into a separatory funnel. The layers were separated, the organics were washed with aqueous Na2SO3 (2 × 50 mL), and the remaining organics were extracted from the aqueous layer using CHCl2 (2 × 50 mL). The mixture was combined, dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexane-25% CHCl2 to give o-iodophenol (3.240 g, 9.340 mmol, 58%) as a clear, colorless, amorphous foam. NMR indicated pure product.

[0206] 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.

[0207] Example 53: Synthesis of Ligand 12 [ka] A mixture of thiophene boropinacolate ester (2.017 g, 2.586 mmol, 3.00 equiv., 72% pure by NMR), KPO (1.647 g, 7.758 mmol, 9.00 equiv.), Pd(AmPhos)Cl (122.0 mg, 0.1724 mmol, 0.20 equiv.), and bisphenyl iodide (0.426 g, 0.8620 mmol, 1.00 equiv.) was prepared. The mixture was evacuated and then refilled with nitrogen. This process was repeated three more times, followed by the sequential addition of deoxygenated 1,4-dioxane (17.0 mL) and deoxygenated water (1.7 mL) via syringe. The mixture was then placed in a heated mantle at 50 °C. After 40 h of vigorous stirring (1000 rpm), the black mixture was removed from the mantle, gradually cooled to 23 °C, suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the clear, black filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed using toluene (2 × 10 mL) by rotary evaporation. The black mixture was then suspended in CHCl (20 mL), suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the black filtrate was concentrated onto Celite and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 50% CHCl in hexane to give the bisthiophene (0.837 g, 0.7544 mmol, 88%) as a red, amorphous oil. NMR indicated a pure product.

[0208] To a solution of the impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (5 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 75% CHCl in hexanes to give the bisthiophene (0.563 g, 0.5668 mmol, 75%, 66% 2 steps) as a light tan solid. NMR indicated pure product.

[0209] 1 H NMR (500MHz, chloroform-d) δ 8.11(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.

[0210] Characterization of the protected coupling product: 1H NMR (500MHz, chloroform-d) δ 8.13(h, J=1.9Hz, 4H), 7.94(ddd, J=7.6, 4.1, 2.3Hz, 2H), 7.49-7.44(m, 4H), 7.38-7.34(m, 6H), 7.34-7.28(m, 2H), 7.08-7.01(m, 4H) , 4.46(t, J=3.0Hz, 4H), 4.30-4.19(m, 4H), 2.79(qt, J=7.2, 2.7Hz, 4H), 2.29-2.20(m, 4H), 1.48(s, 36H), 0.52(tt, J=7.1, 2.9Hz, 6H). 13 C NMR (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.

[0211] Example 54: Synthesis of procatalyst 23 [ka] Ligand 12 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (3.8 mg, 8.20 μmol, 1.10 equiv.) in C6D6 (0.15 mL) was added dropwise to a clear, colorless solution of thiophene (7.4 mg, 7.45 μmol, 1.00 equiv.) in anhydrous C6D6 (1.34 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.005 M solution in C6D6. NMR analysis indicated the product was stable. The same procedure using PhMe as the solvent can be used to prepare procatalyst solutions (0.0025 M or 0.005 M) for polymerization experiments, which are used immediately after filtration.

[0212] 1H NMR (500MHz, ベンゼン-d6) δ 8.48(dd, J=2.0, 0.6Hz, 2H), 8.22(dd, J=1.9, 0.7Hz, 2H), 7.50-7.46(m, 4H), 7.31-7.24 (m, 6H), 6.98-6.96 (m, 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 (126MHz, ベンゼン-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.

[0213] Example 55: Synthesis of プロcatalyst 24

change

[0214] 1 H NMR (500MHz, benzene-d6) δ 8.49(dd, J=2.0, 0.6Hz, 2H), 8.23(dd, J=2.0, 0.6Hz, 2H), 7.47(ddd, J=8.8, 5.0, 1.9Hz, 4H), 7.27(ddd, J=8.5, 4.4 , 1.2Hz, 4H), 7.17(dd, J=8.7, 0.6Hz, 2H), 6.99-6.95(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). 13C 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.

[0215] Example 56: Synthesis of protected hydroxythiophene carbazole intermediates [ka] In a nitrogen-filled, continuously purged glovebox, a mixture of bromothiophene (5.883 g, 24.811 mmol, 1.00 equiv.), 3,6-di-t-butylcarbazole (15.252 g, 54.585 mmol, 2.20 equiv.), CuO (7.100 g, 49.622 mmol, 2.00 equiv.), and KCO (34.290 g, 248.11 mmol, 10.00 equiv.) was suspended in deoxygenated anhydrous xylene (200 mL), N,N'-DMEDA (21.5 mL, 199.84 mmol, 4.00 equiv.) was added, and the mixture was fitted with a reflux condenser and rubber septum, removed from the glovebox, and The mixture was placed under nitrogen, placed in a heated mantle at 140 °C, and stirred vigorously (1000 rpm) for 72 h. It was then removed from the mantle, at which point the deep red-black mixture was gradually cooled to 23 °C, CHCl (100 mL) was added, the mixture was stirred for 5 min, suction filtered over a pad of silica gel, rinsed with CHCl (4 × 75 mL), and the amber filtrate was concentrated onto Celite and purified several times by silica gel chromatography using an ISCO chromatographic purification system with 15% CHCl in hexanes to give the thiophene-carbazole product (7.699 g, 17.673 mmol, 71%) as a white amorphous foam. NMR indicated pure product.

[0216] 1 H NMR (500MHz, chloroform-d) δ 8.12(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=8.6H) z, 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.

[0217] Example 57: Synthesis of Protected Hydroxythiophene Boropinacolate Intermediate [ka] A bright yellow solution of thiophene (3.000 g, 6.887 mmol, 1.00 equiv.) in anhydrous, deoxygenated EtO (75 mL) in a nitrogen-filled, continuously purged glovebox was placed in a freezer (-35 °C) and pre-cooled for 14 h, after which a pre-cooled solution of n-BuLi (3.50 mL, 8.608 mmol, 1.25 equiv., titrated 2.5 M in hexane) was added dropwise rapidly. The pale orange solution was left in the freezer for 4 h, after which isopropoxyboropinacolate ester (2.81 mL, 13.774 mmol, 2.00 equiv.) was added neat. The bright yellow solution was stirred at 23 °C for 2 h, at which point the 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 CHCl (25 mL) and water (25 mL), poured into a separatory funnel, the layers separated, the organics washed with water (1 × 25 mL), the residual organics extracted with CHCl (2 × 25 mL), combined, dried over solid NaSO, decanted, and concentrated. The resulting bright yellow foam was dissolved in CHCl (10 mL), suction filtered through a short pad of silica gel, rinsed with CHCl (4 × 20 mL), and the bright yellow filtrate solution was concentrated to give thiophene-boropinacolate ester (2.581 g, 4.596 mmol, 67%, approximately 72% pure by NMR) as a pale yellow foam. This impure product was used in subsequent reactions without further purification.

[0218] 1 H NMR (500MHz, chloroform-d) δ 8.11-8.08(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, 2 H), 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.

[0219] Example 58: Synthesis of Ligand 13 [ka] A mixture of thiophene boropinacolate ester (1.352 g, 1.806 mmol, 3.00 equiv., 72% pure by NMR), KPO (1.150 g, 5.418 mmol, 9.00 equiv.), Pd(AmPhos)Cl (85.0 mg, 0.1204 mmol, 0.20 equiv.), and bisphenyl iodide (0.330 g, 0.6020 mmol, 1.00 equiv.) was prepared. The mixture was evacuated and then refilled with nitrogen. This process was repeated three more times, followed by the sequential addition of deoxygenated 1,4-dioxane (15.0 mL) and deoxygenated water (1.5 mL) via syringe. The mixture was then placed in a heated mantle at 50 °C. After 40 h of vigorous stirring (1000 rpm), the black mixture was removed from the mantle, gradually cooled to 23 °C, suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the clear, black filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed using toluene (2 × 10 mL) by rotary evaporation. The black mixture was then suspended in CHCl (20 mL), suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the black filtrate was concentrated onto Celite and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 50% CHCl in hexane to give the bisthiophene (0.550 g, 0.4727 mmol, 79%) as a red, amorphous oil. NMR indicated a pure product.

[0220] To a solution of the impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (5 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 75% CHCl in hexanes to give the bisthiophene (0.368 g, 0.3513 mmol, 74%, 59% 2 steps) as a light tan solid. NMR indicated pure product.

[0221] 1 H NMR (400MHz, chloroform-d) δ 8.10(d, J=1.9Hz, 4H), 7.59(dd, J=7.7, 1.7Hz, 2H), 7.43-7.35(m, 6H), 7.28- 7.21(m, 2H), 7.16(d, J=8.6Hz, 4H), 7.13-7.06(m, 4H), 6.82(dd, J=8.3, 1.1Hz , 2H), 4.11(dd, J=9.8, 3.3Hz, 2H), 3.93(dd, J=9.9, 4.3Hz, 2H), 1.83-1.77(m , 2H), 1.72-1.65(m, 2H), 1.63-1.54(m, 2H), 1.43(s, 36H), 1.15-1.00(m, 4H). 13 C NMR (101 MHz, chloroform-d) δ 153.90, 146.54, 142.61, 139.83, 130.67, 128.93, 127.60, 123.51, 123.12, 122.70, 122.60, 120.56, 116.14, 115.34, 113.45, 109.42, 73.64, 40.37, 34.68, 32.01, 29.91, 25.43.

[0222] Characterization of the protected ligand: 1H NMR (500MHz, クロロホルム-d) δ 8.11 (t, J=2.2Hz, 4H), 7.83 (dd, J=7.6, 1.7Hz, 2H), 7.47 (ddd, J=16.4, 8.6, 1.9Hz, 4H), 7 .36-7.30(m, 6H), 7.26-7.21(m, 2H), 6.99(td, J=7.5, 1.1Hz, 2H), 6.93(dd, J=8.4, 1.1Hz, 2H), 4.49-4.38(m, 4H), 4.17-4.02(m, 4H), 2.75(q, J=7.1Hz, 4H), 2.10-1.98(m, 4H), 1.95 -1.85 (m, 2H), 1.60-1.50 (m, 2H), 1.46 (s, 36H), 1.50-1.42 (m, 2H), 0.49 (t, J=7.0Hz, 6H). 13 C NMR (126MHz, クロロホルム-d) δ 156.22, 147.22, 142.71, 139.55, 131.32, 129.31, 124.28, 123.69, 123.65, 123.05, 121.31, 120.36, 11 9.16, 115.94, 111.92, 109.78, 96.91, 71.70, 64.53, 39.60, 34.72, 32.04, 30.48, 26.23, 24.82, 14.16.

[0223] Example 59: Synthesis of プロcatalyst 25

change

[0224] 1 H NMR (500MHz, benzene-d6) δ 8.49(dd, J=2.0, 0.6Hz, 2H), 8.24(dd, J=1.9, 0.6Hz, 2H), 7.54-7.50(m, 2H), 7.48(dd, J=8.6, 2.0Hz, 2H), 7.31 (ddd, J=8.7, 2.0, 0.6Hz, 2H), 7.28(d, J=1.8Hz, 2H), 6.98-6.96(m, 4H), 6.89(s, 2H), 6.81(tt, J=7.4, 1.2Hz, 2 H), 6.77(ddd, J=8.2, 7.4, 1.8Hz, 2H), 6.67(td, J=7.6, 1.1Hz, 2H), 6.63-6.59(m, 2H), 6.26-6.22(m, 4H), 5.18 (dd, J=8.3, 1.1Hz, 2H), 4.17(dd, J=12.6, 8.3Hz, 2H), 3.20(d, J=12.6Hz, 2H), 1.51(s, 18H), 1.42-1.35(m, 2H) 1.30(s, 18H), 1.13-1.06(m, 4H), 0.76-0.69(m, 2H), 0.65-0.58(m, 2H), 0.54(d, J=12.4Hz, 2H), 0.52-0.44(m, 2H). 13C NMR (126 MHz, benzene-d6) δ 156.40, 152.24, 147.22, 143.15, 142.86, 139.15, 138.97, 131.05, 129.79, 128.30, 128.17, 127.36, 126.40, 125.92, 125.23, 124.64, 123.12, 122.71, 122.38, 120.71, 116.84, 116.72, 116.23, 115.50, 112.72, 109.26, 86.21, 75.13, 42.35, 34.59, 34.43, 32.00, 31.80, 31.72, 29.67, 25.35.

[0225] Example 60: Synthesis of procatalyst 26 [ka] Ligand 13 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (5.3 mg, 9.77 μmol, 1.10 equiv.) in C6D6 (0.22 mL) was added dropwise to a clear, colorless solution of thiophene (9.3 mg, 8.88 μmol, 1.00 equiv.) in anhydrous C6D6 (1.56 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.005 M solution in C6D6. NMR analysis indicated the product was stable. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M) for polymerization experiments, which is used immediately after filtration.

[0226] 1H NMR (500MHz, ベンゼン-d6) δ 8.50 (dd, J=2.0, 0.6Hz, 2H), 8.25 (dd, J=2.0, 0.6Hz, 2H), 7.48 (ddd, J=15.6, 8.6, 1.9Hz, 4H), 7.29 (dd, J=8.5, 0.6Hz, 2H), 7.26 (dd, J=7.7, 1.8Hz, 2H), 7.22 (dd, J=8.7, 0.6Hz, 2H), 6.99-6.96 (m, 4H), 6.89 (s, 2H), 6.81-6.76 (m, 4H), 6.68 (td, J=7.6, 1.1Hz, 2H), 6.2 5-6.18 (m, 4H), 5.21 (dd, J=8.3, 1.1Hz, 2H), 4.21 (dd, J=12.6, 8.4Hz, 2H), 3.22 (d, J=12.7Hz, 2H), 1.51 (s, 18H), 1.30 (s, 18H), 1.14 -1.04(m, 4H), 0.91(d, J=13.4Hz, 2H), 0.74(t, J=8.5Hz, 2H), 0.59(d, J=12.7Hz, 2H), 0.46(t, J=10.0Hz, 2H), 0.25(d, J=13.3Hz, 2H). 13 C NMR (126MHz, ベンゼン-d6) δ 155.98, 152.30, 147.83, 143.20, 142.86, 139.16, 138.96, 131.06, 129.76, 128.67, 128.57, 128.18, 127.07, 126.75, 126.12, 124.66, 123.30, 122.68, 122.32, 120.76, 116.87, 116.25, 116.21, 115.44, 112.73, 109.23, 86.74, 78.29, 42.23, 34.60, 34.43, 32.01, 31.73, 29.56, 25.30.

[0227] Example 61: Synthesis of Coordinator 14

change

[0228] To a solution of the impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (5 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 75% CHCl in hexanes to give the bisthiophene (0.280 g, 0.2510 mmol, 68%, 36% 2 steps) as a clear, amorphous foam. NMR indicated pure product.

[0229] 1 H NMR (400MHz, chloroform-d) δ 8.18-8.12(m, 4H), 7.41(dd, J=8.6, 1.9Hz, 4H), 7.33(s, 2H), 7.14(dd, J=8.5, 0.6Hz, 4H), 7.07(dd, J=9.2, 3.1Hz, 2H), 6.55-6.45(m, 4H), 6.21(dd, J=9.2, 4.6Hz, 2H), 3.72(s, 4H), 1.46(s, 36H), 1.08-0.95(m, 2H), 0.88(d, J=7.3Hz, 12H). 19 F NMR (376 MHz, chloroform-d) δ −121.90 (td, J = 8.5, 4.7 Hz). 13 C NMR (101 MHz, chloroform-d) δ 157.34 (d, J = 240.5 Hz), 152.56 (d, J = 2.2 Hz), 146.63, 142.86, 139.79, 127.10, 123.54, 123.20, 122.96 (d, J = 8.5 Hz), 120.74, 116.56 (d, J = 24.4 Hz), 116.07, 115.07 (d, J = 23.2 Hz), 114.22 (d, J = 1.9 Hz), 114.08 (d, J = 8.8 Hz), 109.53, 58.54, 34.72, 32.03, 17.90, 9.71.

[0230] Characterization of the protected ligand: 1 H NMR (500MHz, chloroform-d) δ 8.13(d, J=2.0Hz, 4H), 7.49(ddd, J=8.6, 6.2, 2.5Hz, 6H), 7.36(s, 2H), 7.27(d, J=8.6Hz, 4H), 6.90(dtd, J=11.9, 9.0, 3.8Hz, 4H), 4 .36(s, 4H), 3.98(s, 4H), 2.75(q, J=6.9Hz, 4H), 1.48(s, 36H), 1.41(t, J=7.7Hz, 2H), 1.17(d, J=7.5Hz, 12H), 0.54(t, J=7.1Hz, 6H). 19 F NMR (470 MHz, chloroform-d) δ −124.28 (td, J = 8.5, 4.6 Hz). 13 C NMR (126 MHz, chloroform-d) δ 156.50(d, J=238.5Hz), 154.65(d, J=1.9Hz), 147.53, 142.90, 139.51, 12 9.24, 123.69, 123.12, 123.09(d, J=1.8Hz), 122.11(d, J=8.5Hz), 119.81, 118.12(d, J=24.0Hz), 116.03, 115.29(d, J=22.8Hz), 111.98(d, J=8.3Hz) , 109.70, 96.85, 64.63, 56.85, 34.74, 32.04, 24.82, 18.26, 14.20, 10.09.

[0231] Example 62: Synthesis of procatalyst 27 [ka] Ligand 14 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (4.1 mg, 9.07 μmol, 1.10 equiv.) in C6D6 (0.33 mL) was added dropwise to a clear, colorless solution of thiophene (9.2 mg, 8.25 μmol, 1.00 equiv.) in anhydrous C6D6 (2.97 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to yield the zirconium complex as a 0.0025 M solution in C6D6. NMR indicated the product. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.0025 M) to be used immediately after filtration in polymerization experiments.

[0232] 1 H NMR (500MHz, benzene-d6) δ 8.45(dd, J=1.9, 0.6Hz, 2H), 8.30(dd, J=1.9, 0.6Hz, 2H), 7.55(dd, J=8.7, 1.9Hz, 2H), 7.50(dd, J=8.5, 1.9Hz, 2H), 7.40(dd, J=8.7 , 0.7Hz, 2H), 7.33(dd, J=8.5, 0.6Hz, 2H), 7.06-7.02(m, 2H), 6.99-6.92(m, 4H), 6.84(s, 2H), 6.80-6.74(m, 2H), 6.62(ddd, J=9.0, 7 .3, 3.1Hz, 2H), 6.37-6.34(m, 4H), 5.37(dd, J=9.0, 4.8Hz, 2H), 4.17(d, J=14.7Hz, 2H), 3.15(d, J=14.8Hz, 2H), 1.40(s, 18H), 1.28 (s, 18H), 1.12(d, J=12.5Hz, 2H), 0.58(d, J=12.5Hz, 2H), 0.52(d, J=7.1Hz, 6H), 0.42(d, J=6.5Hz, 6H), 0.37(tt, J=8.0, 6.0Hz, 2H). 19 F NMR (470 MHz, benzene-d6) δ −115.88 (td, J = 7.8, 4.5 Hz). 13C NMR (126MHz, benzene-d6) δ 159.41(d, J=245.7Hz), 154.25, 154.23, 152.87, 146.47, 143.27(d, J=52.4Hz), 139.70(d, J=31.6Hz), 130.56, 128.33, 128.16, 126.41, 125.21, 124.60, 124.12, 122.82, 122.52, 122. 29(d, J=9.1Hz), 121.24, 119.11, 116.65, 116.35, 116.19(d, J=13.2Hz), 116.00(d, J=13.5H z), 115.64, 112.22, 108.99, 75.76, 70.55, 34.54, 34.45, 31.89, 31.69, 17.55, 17.51, 9.44.

[0233] Example 63: Synthesis of procatalyst 28 [ka] Ligand 14 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (4.8 mg, 8.78 μmol, 1.10 equiv.) in C6D6 (0.39 mL) was added dropwise to a clear, colorless solution of thiophene (8.9 mg, 7.98 μmol, 1.00 equiv.) in anhydrous C6D6 (2.81 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.0025 M solution in C6D6. NMR indicated the product. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.0025 M) to be used immediately after filtration in polymerization experiments.

[0234] 1H NMR (500MHz, ベンゼン-d6) δ 8.46 (dd, J=1.9, 0.6Hz, 2H), 8.31 (dd, J=1.9, 0.6Hz, 2H), 7.54 (dd, J=8.7, 1.9Hz, 2H), 7.49 (dd, J=8.5, 1.9Hz, 2H), 7.3 2 (ddd, J=10.9, 8.6, 0.6Hz, 4H), 6.99-6.89 (m, 6H), 6.84 (s, 2H), 6.78-6.71 (m, 2H), 6.65 (ddd, J=9.0, 7.3, 3.1Hz, 2H), 6.40-6.35 (m, 4H), 5.39 (dd, J=9.0, 4.7Hz, 2H), 4.20 (d, J=14.8Hz, 2H), 3.15 (d, J=14.8Hz, 2H), 1.40 (s, 18H), 1.28 (s, 18H), 1.01 (d, J=13.6Hz, 2H), 0.50 (d, J=7.1Hz, 6H), 0.40 (d, J=7.1Hz, 6H), 0.39-0.30 (m, 2H), 0.27 (d, J=13.6Hz, 2H). 19 F NMR (470MHz, ベンゼン-d6) δ -115.48 (td, J=8.1, 4.8Hz). 13 C NMR (126MHz, ベンゼン-d6) δ 159.61(d, J=246.2Hz), 153.86(d, J=2.7Hz), 152.98, 147.22, 143.32(d, J=61.0Hz), 139.69 (d, J=36.3Hz), 138.52, 129.89, 128.61, 127.17, 126.71, 124.65, 124.35, 122.78, 122.71 (d, J=8.9Hz), 122.46, 121.25, 119.23, 116.32, 116.17 (d, J=10.2Hz), 115.98 (d, J=9.8Hz), 115 .95, 115.55, 112.30, 108.98, 83.00, 71.02, 34.54, 34.45, 31.89, 31.69, 17.49, 17.45, 9.50.

[0235] Example 64: Synthesis of bridging intermediate of ligand 13

change

[0236] 1 H NMR (500MHz, chloroform-d) δ 7.76(dd, J=7.9, 1.6Hz, 2H), 7.26(td, J=7.8, 1.6Hz, 2H), 6.82(dd, J=8.2, 1.3Hz, 2H), 6.69(td, J=7.6, 1.4Hz, 2H), 4.10-3.98(m, 4H) , 2.01 (ddt, J=25.4, 13.2, 2.9Hz, 4H), 1.86 (dq, J=8.4, 2.9Hz, 2H), 1.52 (dd, J=17.3, 7.8Hz, 2H), 1.41 (ddt, J=12.0, 8.9, 4.9Hz, 2H). 13 C NMR (126 MHz, chloroform-d) δ 157.47, 139.27, 129.46, 122.24, 111.89, 86.52, 72.02, 39.71, 30.29, 26.16.

[0237] Example 65: Synthesis of a bridging intermediate for ligand 13 [ka] A white heterogeneous mixture of iodophenol (0.458 g, 2.082 mmol, 1.05 equiv.), K2CO3 (0.863 g, 6.246 mmol, 3.15 equiv.), and monotosylate (0.992 g, 1.982 mmol, 1.00 equiv.) in acetone (25 mL) under nitrogen and equipped with a reflux condenser was placed in a heated mantle at 60 °C and stirred (500 rpm) for 48 h. After stirring, the white heterogeneous mixture was removed from the mantle and 23 The mixture was cooled to °C, diluted with CHCl (50 mL), stirred vigorously (1000 rpm) for 5 min, suction filtered through a Celite pad, rinsed with CHCl (3 × 25 mL), and the resulting filtrate solution was concentrated onto Celite and purified by silica gel chromatography using 10% CHCl in hexanes to 75% CHCl in hexanes to give the bis-iodophenyl ether (0.677 g, 1.235 mmol, 62%) as a white solid. NMR of each indicated pure product.

[0238] 1 H NMR (500MHz, chloroform-d) δ 7.76(dd, J=7.9, 1.6Hz, 2H), 7.26(td, J=7.8, 1.6Hz, 2H), 6.82(dd, J=8.2, 1.3Hz, 2H), 6.69(td, J=7.6, 1.4Hz, 2H), 4.10-3.98(m, 4H) , 2.01 (ddt, J=25.4, 13.2, 2.9Hz, 4H), 1.86 (dq, J=8.4, 2.9Hz, 2H), 1.52 (dd, J=17.3, 7.8Hz, 2H), 1.41 (ddt, J=12.0, 8.9, 4.9Hz, 2H). 13 C NMR (126 MHz, chloroform-d) δ 157.47, 139.27, 129.46, 122.24, 111.89, 86.52, 72.02, 39.71, 30.29, 26.16.

[0239] Example 66: Synthesis of Ligand 15 [ka] A mixture of thiophene boropinacolate ester (2.017 g, 2.586 mmol, 3.00 equiv., 72% pure by NMR), KPO (1.647 g, 7.758 mmol, 9.00 equiv.), Pd(AmPhos)Cl (122.0 mg, 0.1724 mmol, 0.20 equiv.), and bisphenyl iodide (0.478 g, 0.8620 mmol, 1.00 equiv.) was prepared. The mixture was evacuated and then refilled with nitrogen. This process was repeated three more times, followed by the sequential addition of deoxygenated 1,4-dioxane (17.0 mL) and deoxygenated water (1.7 mL) via syringe. The mixture was then placed in a heated mantle at 50 °C. After 40 h of vigorous stirring (1000 rpm), the black mixture was removed from the mantle, gradually cooled to 23 °C, suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the clear, black filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed using toluene (2 × 10 mL) by rotary evaporation. The black mixture was then suspended in CHCl (20 mL), suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the black filtrate was concentrated onto Celite and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 50% CHCl in hexane to give the bisthiophene (0.747 g, 0.6387 mmol, 74%) as a red, amorphous oil. NMR indicated a pure product.

[0240] To a solution of the impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (5 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 75% CHCl in hexanes to give the bisthiophene (0.514 g, 0.4879 mmol, 76%, 57% 2 steps) as a light tan solid. NMR indicated pure product.

[0241] 1 H NMR (500MHz, chloroform-d) δ 8.14(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=2.9Hz, 2H), 6. 84(d, J=9.0Hz, 2H), 6.79(dd, J=8.9, 2.9Hz, 2H), 3.99(q, J=3.5, 2.1Hz, 4H), 3.84(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.

[0242] Characterization of the protected ligand: 1H NMR (500MHz, chloroform-d) δ 8.10(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, 3.1 Hz, 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.

[0243] Example 67: Synthesis of procatalyst 29 [ka] Ligand 15 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (3.7 mg, 7.72 μmol, 1.10 equiv.) in C6D6 (0.16 mL) was added dropwise to a clear, colorless solution of thiophene (7.4 mg, 7.02 μmol, 1.00 equiv.) in anhydrous C6D6 (1.25 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.005 M solution in C6D6. NMR analysis indicated the product was stable. The same procedure using PhMe as the solvent can be used to prepare procatalyst solutions (0.0025 M or 0.005 M) for polymerization experiments, which are used immediately after filtration.

[0244] 1H NMR (400MHz, ベンゼン-d6) δ 8.47 (dd, J=2.0, 0.6Hz, 2H), 8.24 (dd, J=1.9, 0.6Hz, 2H), 7.49 (td, J=8.6, 1.9Hz, 4H), 7.30 (ddd, J=8.5, 5.3, 0.6Hz, 4H ), 7.08-7.03 (m, 2H), 6.96 (dtd, J=6.9, 1.4, 0.7Hz, 2H), 6.92 (d, J=3.1Hz, 2H), 6.84 (s, 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), 3.16 (s, 6H), 1.47 (s, 18H), 1.27 (s, 18H), 1.08 (d, J=12.3Hz, 2H), 0.88-0.74 (m, 2H), 0.58 (d, J=12.3Hz, 2H), 0.56-0.51 (m, 2H). 13 C NMR (101MHz, ベンゼン-d6) δ 157.39, 152.38, 149.56, 147.35, 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.

[0245] Example 68: Synthesis of プロcatalyst 30

change

[0246] 1 H NMR (500MHz, benzene-d6) δ 8.50(dd, J=2.0, 0.6Hz, 2H), 8.26(dd, J=1.9, 0.6Hz, 2H), 7.50(dd, J=2.5, 1.9Hz, 2H), 7.48(t, J=2.1Hz, 2H), 7.29( dd, J=8.5, 0.6Hz, 2H), 7.23(dd, J=8.7, 0.6Hz, 2H), 6.99-6.95(m, 2H), 6.93(d, J=3.1Hz, 2H), 6.85(s, 2H), 6.79-6.7 4(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). 13C NMR (126 MHz, benzene-d6) δ 157.52, 152.44, 149.28, 148.02, 143.20, 142.73, 139.32, 139.12, 129.89, 128.60, 128.57, 128.03, 127.04, 126.83, 124.63, 124.35, 122.58, 122.30, 120.69, 117.13, 116.30, 115.70, 115.48, 114.96, 112.58, 108.91, 83.01, 78.24, 54.76, 34.57, 34.43, 32.00, 31.73, 26.04.

[0247] Example 69: Synthesis of bis-4-methoxy-2-iodophenyl ether [ka] A white heterogeneous mixture of 2-iodophenol (1.890 g, 7.559 mmol, 2.00 equiv.), K2CO3 (3.134 g, 22.677 mmol, 6.00 equiv.), and 1,4-dibromobutane (0.45 mL, 3.779 mmol, 1.00 equiv.) in acetone (40 mL) under nitrogen and equipped with a reflux condenser was placed in a heated mantle at 60 °C and stirred (500 rpm) for 36 h. After stirring, the white heterogeneous mixture was removed from the mantle. The mixture was cooled to 23 °C, diluted with CHCl (50 mL), stirred for 2 min, and suction filtered through a Celite pad, rinsing with CHCl (4 × 20 mL). The resulting pale yellow filtrate was concentrated onto Celite and purified by silica gel chromatography using an ISCO chromatographic purification system with 50–100% CHCl in hexanes to give the iodophenyl ether (1.945 g, 3.510 mmol, 93%) as a white solid. NMR indicated pure product.

[0248] 1 H NMR (500MHz, chloroform-d) δ 7.32(d, J=2.9Hz, 2H), 6.84(dd, J=8.9, 3.0Hz, 2H), 6.76(d, J=8.9Hz, 2H), 4.11-3.99(m, 4H), 3.75(s, 6H), 2.13-2.01(m, 4H). 13C NMR (126 MHz, chloroform-d) δ 154.26, 152.05, 124.61, 114.78, 113.06, 86.94, 69.58, 55.92, 26.15.

[0249] Example 70: Synthesis of 4-methoxy-2-iodophenol [ka] 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, 1N) in methanol (300 mL) and water (200 mL) under nitrogen was placed in an ice bath and stirred vigorously for 1 h, after which pre-chilled commercial aqueous bleach (61 mL, 42.291 mmol, 1.05 equiv, 5.2% w / w) was added dropwise over 30 min. At this point, the dark orange mixture was stirred at 0 °C for 30 min. The mixture was removed from the ice-water bath, and solid NaH2PO4 (30 g) was added, followed by aqueous Na2SO3 (200 mL) to reduce residual iodine and water (200 mL). The mixture was stirred vigorously for 10 min, diluted with CHCl2 (50 mL), and the biphasic dark red-orange mixture was poured into a separatory funnel. The layers were separated, and the organics were washed with aqueous Na2SO3 (2 × 50 mL). The remaining organics were extracted from the aqueous layer using CHCl2 (2 × 50 mL), combined, dried over solid Na2SO4, decanted, and concentrated to give a reddish-brown viscous oil. NMR showed the starting phenol and observable product, albeit in small amounts, in a ca. 70:30 SM:product mixture, with other decomposition adducts present. The crude mixture was dissolved in CHCl, concentrated onto Celite, and purified by silica gel chromatography using 25% CHCl to 100% CHCl in hexanes to give O-iodophenol (0.877 g, 3.508 mmol, 9%) as a pale purple amorphous foam, and recovered starting phenol (1.277 g, 10.287 mmol, 26%). NMR indicated pure product.

[0250] 1H NMR (500 MHz, chloroform-d) δ 7.18 (d, J = 2.9 Hz, 1H), 6.90 (d, J = 8.9 Hz, 1H), 6.83 (dd, J = 8.9, 2.9 Hz, 1H), 5.00 (s, 1H), 3.74 (s, 3H). 13 C NMR (126 MHz, chloroform-d) δ 153.93, 149.17, 122.66, 116.37, 115.13, 85.07, 55.99.

[0251] Example 71: Synthesis of Ligand 16 [ka] A mixture of thiophene boropinacolate ester (0.605 g, 0.5387 mmol, 2.70 equiv., 50% pure by NMR), KPO (0.343 g, 1.616 mmol, 8.10 equiv.), Pd(AmPhos)Cl (28.3 mg, 0.0399 mmol, 0.20 equiv.), and bisphenyl iodide (0.143 g, 0.2000 mmol, 1.00 equiv.) was prepared. The mixture was evacuated and then refilled with nitrogen. This process was repeated three more times. Deoxygenated 1,4-dioxane (4.0 mL) and deoxygenated water (0.4 mL) were then added sequentially via syringe. The mixture was then placed in a heated mantle at 50 °C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was removed from the mantle, gradually cooled to 23 °C, suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the clear, black filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed using toluene (2 × 10 mL) by rotary evaporation. The black mixture was then suspended in CHCl (20 mL), suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the black filtrate was concentrated onto Celite and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 50% CHCl in hexanes to give the bisthiophene (0.168 g) as an off-white solid. NMR indicated the product contained a small amount of impurity. This material was used for subsequent deprotection without further purification.

[0252] To a solution of the impure coupled product in CHCl-1,4-dioxane (8 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (4 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 50% CHCl in hexanes to give the bisthiophene (80.0 mg, 0.0657 mmol, 33% yield, 2 steps) as a light tan solid. NMR indicated a pure product.

[0253] 1 H NMR (400MHz, chloroform-d) δ 8.11(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.

[0254] Example 72: Synthesis of procatalyst 31 [ka] Ligand 16 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (3.0 mg, 6.69 μmol, 1.10 equiv.) in C6D6 (0.13 mL) was added dropwise to a clear, colorless solution of thiophene (7.4 mg, 6.08 μmol, 1.00 equiv.) in anhydrous C6D6 (1.09 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.005 M solution in C6D6. NMR indicated the product. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M) to be used immediately after filtration in polymerization experiments.

[0255] 1 H NMR (400MHz, benzene-d6) δ 8.55(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, 4) H), 5.17(d, J=8.7Hz, 2H), 4.08-3.98(m, 2H), 3.42-3.34(m, 2H), 1.68(d, J=14.6Hz, 2H), 1.57(s, 18H), 1.51(d, J=14.6Hz, 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). 13C 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.

[0256] Example 73: Synthesis of procatalyst 32 [ka] Ligand 16 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (4.1 mg, 7.50 μmol, 1.10 equiv.) in C6D6 (0.17 mL) was added dropwise to a clear, colorless solution of thiophene (8.3 mg, 6.82 μmol, 1.00 equiv.) in anhydrous C6D6 (1.19 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.005 M solution in C6D6. NMR analysis indicated the product was stable. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M) for polymerization experiments, which is used immediately after filtration.

[0257] 1H NMR (500MHz, ベンゼン-d6) δ 8.57 (dd, J=1.9, 0.6Hz, 2H), 8.15 (dd, J=2.0, 0.7Hz, 2H), 7.58 (d, J=2.5Hz, 2H), 7.52 (dd, J=8.5, 1.9Hz, 2H), 7.42 (dd, J=8.7, 1.9Hz, 2H), 7.33(dd, J=8.5, 0.6Hz, 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), 6.24-6.18(m, 4H), 5 .21(d, J=8.7Hz, 2H), 4.15-4.06(m, 2H), 3.50-3.41(m, 2H), 1.69(d, J=14.6Hz, 2H), 1.59(s, 18H), 1.53(d, J=14.7Hz, 2H), 1.25(s, 18 H), 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). 13 C NMR (126MHz, ベンゼン-d6) δ 153.62, 152.32, 149.13, 147.76, 142.98, 142.63, 139.24, 139.11, 128.73, 128.66, 128.04, 127.05, 126.99, 126.92, 125.36, 124.67, 122.99, 122.61, 1 22.21, 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.

[0258] Example 74: Synthesis of Coordinator 17

change

[0259] To a solution of the impure coupled product in CHCl-1,4-dioxane (6 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (3 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 75% CHCl in hexanes to give the bisthiophene (52.0 mg, 0.05052 mmol, 25% yield, two steps) as a light tan solid. NMR indicated a pure product.

[0260] 1 H NMR (400MHz, chloroform-d) δ 8.10(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 (101MHz, chloroform-d) δ 158.08(d, J=241.4Hz), 149.83(d, J=2.3Hz), 146.99, 142.85, 139.52, 127.55, 124.80(d, J=8.6Hz), 123.50, 123.21, 120.82, 116 .56(d, J=24.7Hz), 116.24, 115.69(d, J=8.8Hz), 114.72(d, J=23.3Hz), 114.00(d, J=1.8Hz), 109.47, 70.96, 34.68, 31.99, 25.83.

[0261] Characterization of the protected ligand: 1H NMR (400MHz, chloroform-d) δ 8.08(dd, J=1.9, 0.7Hz, 4H), 7.78(dd, J=9.7, 2.9Hz, 2H), 7.42(dd, J=8.6, 1.9Hz, 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=7.0Hz, 4H), 2.25-2.15(m, 4H), 1.43(s, 38H), 0.55(t, J=7.1Hz, 6H). 19 F NMR (376 MHz, chloroform-d) δ −123.44 (ddd, J = 9.9, 7.4, 4.8 Hz).

[0262] Example 75: Synthesis of procatalyst 33 [ka] Ligand 17 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (4.5 mg, 9.83 μmol, 1.10 equiv.) in C6D6 (0.18 mL) was added dropwise to a clear, colorless solution of thiophene (9.2 mg, 8.94 μmol, 1.00 equiv.) in anhydrous C6D6 (1.61 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.005 M solution in C6D6. NMR analysis indicated the product was stable. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M) to be used immediately after filtration in polymerization experiments.

[0263] 1H NMR (500MHz, ベンゼン-d6) δ 8.42(dd, J=2.0, 0.6Hz, 2H), 8.28(dd, J=1.9, 0.7Hz, 2H), 7.51(dd, J=8.7, 1.9Hz, 2H), 7.44(dd, J=8.5, 1.9Hz, 2H), 7.33(d d. 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, 4.6 Hz, 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 F NMR (470MHz, ベンゼン-d6) δ -114.74--117.39(m). 13 C NMR (126MHz, ベンゼン-d6) δ 159.84(d, J=246.8Hz), 152.62, 151.81(d, J=2.6Hz), 146.41, 143.19(d, J=49.2Hz), 139.19( d, J=20.1Hz), 130.56, 128.33, 128.06, 126.53, 125.18, 124.92 (d, J=8.9Hz), 124.30 (d, J=47. 3Hz), 122.56 (d, J=38.4Hz), 121.16, 118.06, 116.69 (d, J=47.1Hz), 116.69, 115.98 (d, J=91. 0Hz), 115.83 (d, J=1.9Hz), 112.30, 108.75, 74.98, 72.01, 34.52, 34.45, 31.94, 31.72, 25.71.

[0264] Example 76: Synthesis of プロcatalyst 34

change

[0265] 1 H NMR (500MHz, benzene-d6) δ 8.43(dd, J=2.0, 0.6Hz, 2H), 8.29(dd, J=1.9, 0.6Hz, 2H), 7.49(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(tt, J=7.5, 1 .3Hz, 2H), 6.55-6.47(m, 4H), 6.30-6.25(m, 4H), 5.01(dd, J=9.0, 4.8Hz, 2H), 3.89-3.78(m, 2H), 3.15(dd, J=12.4, 4.7Hz , 2H), 1.43(s, 18H), 1.30(s, 18H), 0.90(d, J=13.4Hz, 2H), 0.73-0.62(m, 2H), 0.49-0.40(m, 2H), 0.24(d, J=14.0Hz, 2H). 19 F NMR (470 MHz, benzene-d6) δ -115.11--115.24 (m). 13C NMR (126MHz, ベンゼン-d6) δ 159.97(d, J=247.4Hz), 152.66, 151.46(d, J=2.7Hz), 147.32, 143.24(d, J=55.5Hz), 13 9.14(d, J=26.6Hz), 138.52, 130.56, 128.38(d, J=11.1Hz), 127.15, 126.72, 124.55, 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.

[0266] Example 77: Synthesis of Coordinator 18

change

[0267] To a solution of the impure coupled product in CHCl-1,4-dioxane (6 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (3 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 75% CHCl in hexanes to give the bisthiophene (0.105 g, 0.09856 mmol, 49% yield, 2 steps) as a clear, amorphous foam. NMR indicated a pure product.

[0268] 1 H NMR (400MHz, chloroform-d) δ 8.12(dd, J=1.9, 0.6Hz, 4H), 7.56(dd, J=11.4, 8.8Hz, 2H), 7.39(dd, J=8.6, 1.9Hz, 4H), 7.30(s, 2H), 7.17(dd, J=8 .6, 0.6Hz, 4H), 6.74(dd, J=11.4, 6.8Hz, 2H), 6.54(s, 2H), 4.06-3.97(m, 4H), 1.95(p, J=2.5Hz, 4H), 1.42(s, 36H). 19 F NMR (376 MHz, chloroform-d) δ −135.22 (ddd, J = 22.5, 11.5, 8.8 Hz), −144.91 (ddd, J = 22.2, 11.2, 6.8 Hz). 13 C NMR (101 MHz, chloroform-d) δ 150.19-149.71 (m), 149.36 (dd, J = 250.5, 13.9 Hz), 146.75-144.02 (m), 146.55, 143.08, 139.43, 127.14, 123.61, 123.29, 120.52, 119.32-118.89 (m), 118.15 (d, J = 20.6 Hz), 116.34, 112.97, 109.37, 103.52 (d, J = 20.8 Hz), 70.59, 34.70, 31.97, 25.83.

[0269] Example 78: Synthesis of procatalyst 35 [ka] Ligand 18 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (5.3 mg, 11.56 μmol, 1.10 equiv.) in C6D6 (0.42 mL) was added dropwise to a clear, colorless solution of thiophene (11.2 mg, 10.51 μmol, 1.00 equiv.) in anhydrous C6D6 (3.78 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.0025 M solution in C6D6. NMR analysis indicated the product was stable. The same procedure using PhMe as the solvent can be used to prepare procatalyst solutions (0.0025 M or 0.005 M) for polymerization experiments, which are used immediately after filtration. Slow and gradual evaporation of the NMR solution resulted in the crystallization of the zirconium complex, which was characterized using X-ray diffraction to unambiguously confirm the structure.

[0270] 1H NMR (500MHz, ベンゼン-d6) δ 8.55 (d, J=1.9Hz, 1H), 8.46 (d, J=1.9Hz, 1H), 8.39 (t, J=1.3Hz, 1H), 8.33 (dd, J= 2.0, 0.7Hz, 1H), 7.58(d, J=1.3Hz, 2H), 7.52(ddd, J=8.5, 6.7, 1.9Hz, 3H), 7.47(d d, J=8.7, 0.7Hz, 1H), 7.23-7.20(m, 2H), 7.08-7.02(m, 3H), 6.96-6.94(m, 2H), 6 .93(s, 1H), 6.82(s, 1H), 6.80-6.72(m, 3H), 6.54-6.48(m, 2H), 6.29-6.24(m, 2H) ,5.67(dd,J=10.8,6.9Hz,1H),5.00-4.91(m,1H),3.80-3.71(m,1H),3.04(dd,J =12.5, 3.7Hz, 1H), 2.68 (dd, J=11.4, 7.2Hz, 1H), 2.11 (d, J=10.1Hz, 1H), 1.53 (s, 9H), 1.27(d, J=1.2Hz, 18H), 1.25(s, 9H), 0.96(d, J=12.0Hz, 2H), 0.93-0.83(m, 1H), 0.71-0.63(m, 1H), 0.63-0.58(m, 2H), 0.57-0.52(m, 1H), 0.38-0.27(m, 1H).

[0271] 19 F NMR (470MHz, ベンゼン-d6) δ -131.71(dt, J=23.0, 9.6Hz), -134.32(dt, J=19.7, 9.7Hz), -136.51--137.09(m), -138.80(ddd, J=22.8, 10.4, 6.9Hz).

[0272] Example 79: Synthesis of プロcatalyst 36

change

[0273] 1 H NMR (500MHz, benzene-d6) δ 8.57(d, J=1.9Hz, 2H), 8.33(dd, J=2.0, 0.6Hz, 2H), 7.54-7.48(m, 4H), 7.41(dd, J=8.7, 0.6Hz, 2H), 7.19(d d, J=8.4, 0.6Hz, 2H), 6.99-6.95(m, 2H), 6.82(s, 2H), 6.79(dd, J=10.5, 8.6Hz, 2H), 6.77-6.70(m, 2H), 6.5 3-6.48(m, 2H), 6.36-6.32(m, 4H), 4.98(dd, J=10.5, 7.0Hz, 2H), 3.76-3.65(m, 2H), 3.07-2.99(m, 2H), 1.5 3(s, 18H), 1.26(s, 18H), 1.00(d, J=13.5Hz, 2H), 0.67-0.58(m, 2H), 0.52-0.43(m, 2H), 0.37-0.31(m, 2H). 19 F NMR (470 MHz, benzene-d6) δ −131.68 (dt, J = 23.1, 9.5 Hz), −138.29 (ddd, J = 23.0, 10.7, 7.2 Hz).

[0274] Example 80: Synthesis of bis-4,5-difluoro-2-iodophenyl ether [ka] A white heterogeneous mixture of iodophenol (5.700 g, 22.266 mmol, 2.00 equiv.), K2CO3 (9.232 g, 66.799 mmol, 6.00 equiv.), and 1,4-dibromobutane (1.33 mL, 11.133 mmol, 1.00 equiv.) in acetone (100 mL) under nitrogen and equipped with a reflux condenser was placed in a heated mantle at 60 °C and stirred (500 rpm) for 36 h. After stirring, the white heterogeneous mixture was removed from the mantle. The mixture was cooled to 23 °C, diluted with CHCl (50 mL), stirred vigorously (1000 rpm) for 5 min, suction filtered through a Celite pad, rinsed with CHCl (3 × 25 mL), and the resulting filtrate solution was concentrated onto Celite and purified by silica gel chromatography using 10% CHCl in hexanes - 50% CHCl in hexanes to give the bis-iodophenyl ether (5.798 g, 10.243 mmol, 92%) as a white solid. NMR indicated the product.

[0275] 1 H NMR (500MHz, chloroform-d) δ 7.57(t, J=9.0Hz, 2H), 6.67(dd, J=11.9, 6.7Hz, 2H), 4.05(d, J=5.3Hz, 4H), 2.10(q, J=4.9, 3.7Hz, 4H). 19 F NMR (470 MHz, chloroform-d) δ −134.17 (ddd, J = 21.0, 12.1, 8.8 Hz), −145.86 (dt, J = 21.0, 8.2 Hz). 13 C NMR (126 MHz, chloroform-d) δ 154.03 (dd, J = 7.6, 2.4 Hz), 150.52 (dd, J = 249.2, 13.5 Hz), 144.64 (dd, J = 245.3, 13.1 Hz), 126.87 (d, J = 20.4 Hz), 101.50 (d, J = 21.5 Hz), 77.77 (dd, J = 6.1, 4.0 Hz), 69.55, 25.86.

[0276] Example 81: Synthesis of 4,5-difluoro-2-iodophenol [ka] A clear, colorless solution of the starting phenol (5.000 g, 38.434 mmol, 1.00 equiv), KI (10.846 g, 65.337 mmol, 1.70 equiv), and aqueous NaOH (65 mL, 65.337 mmol, 1.70 equiv, 1N) in methanol (200 mL) and water (50 mL) under nitrogen was placed in an ice bath and vigorously stirred (1000 rpm) for 1 h, after which pre-chilled commercial aqueous bleach (84 mL, 65.337 mmol, 1.70 equiv, 5.2% w / w) was added dropwise over 10 min. At this point, the bright yellow solution was stirred at 0 °C for 2 h. The mixture was removed from the ice-water bath and stirred at 23 °C for 4 h. Solid KH2PO4 (25 g) was added, followed by the addition of saturated aqueous Na2SO3 (100 mL) to reduce residual iodine. Water (100 mL) was added. The mixture was stirred vigorously for 10 min, diluted with CHCl2 (50 mL), and the biphasic yellow mixture was poured into a separatory funnel. The layers were separated, the organics were washed with aqueous Na2SO3 (2 × 50 mL), and the residual organics were extracted from the aqueous layer using CHCl2 (2 × 25 mL). The mixture was combined, dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexanes-50% CHCl2 in hexanes to give o-iodophenol (5.742 g, 22.431 mmol, 58%) as a clear, light brown, viscous oil. NMR indicated pure product.

[0277] 1 H NMR (500 MHz, chloroform-d) δ 7.45 (dd, J = 9.2, 8.4 Hz, 1H), 6.86 (dd, J = 11.3, 7.0 Hz, 1H), 5.16 (s, 1H). 19 F NMR (470 MHz, chloroform-d) δ −133.85 (dp, J = 20.7, 10.3, 9.5 Hz), −145.38 (tq, J = 20.8, 8.2, 7.7 Hz). 13C NMR (126MHz, chloroform-d) δ 151.61(dd, J=9.9, 2.7Hz), 151.13(dd, J=249.5, 13.6Hz), 144.79(dd, J=245.8, 13.5Hz), 125.24(d, J=20.5Hz), 103.94(d, J=21.1Hz), 76.65(dd, J=6.6, 4.1Hz).

[0278] Example 82: Synthesis of Ligand 19 [ka] A mixture of thiophene boropinacolate ester (0.605 g, 0.5387 mmol, 2.70 equiv., 50% pure by NMR), KPO (0.343 g, 1.616 mmol, 8.10 equiv.), Pd(AmPhos)Cl (28.0 mg, 0.0399 mmol, 0.20 equiv.), and bisphenyl iodide (0.120 g, 0.1995 mmol, 1.00 equiv.) was prepared. The mixture was evacuated and then refilled with nitrogen. This process was repeated three more times. Deoxygenated 1,4-dioxane (4.0 mL) and deoxygenated water (0.4 mL) were then added sequentially via syringe. The mixture was then placed in a heated mantle at 50 °C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was removed from the mantle, gradually cooled to 23 °C, suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the clear, black filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed using toluene (2 × 10 mL) by rotary evaporation. The black mixture was then suspended in CHCl (20 mL), suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the black filtrate was concentrated onto Celite and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 60% CHCl in hexane to give impure bisthiophene (0.201 g) as a bright yellow foam. NMR indicated the product contained impurities. This impure material was used in subsequent reactions.

[0279] To a solution of the impure coupled product in CHCl-1,4-dioxane (6 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (3 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 75% CHCl in hexanes to give the bisthiophene (0.107 g, 0.09716 mmol, 49% yield, 2 steps) as a clear, amorphous foam. NMR indicated a pure product.

[0280] 1 H NMR (500MHz, chloroform-d) δ 8.13(d, J=1.9Hz, 4H), 7.44-7.36(m, 6H), 7.18(d, J=8.6Hz, 4H), 6.52(ddd, J=11.6, 6.1 , 1.9Hz, 2H), 5.57(s, 2H), 3.93-3.88(m, 4H), 1.84(q, J=2.8, 2.3Hz, 4H), 1.44(s, 36H). 19 F NMR (470MHz, chloroform-d) δ -130.70(dd, J=22.3, 6.5Hz), -132.47(ddd, J=22.4, 11.5, 6.7Hz), -167.89(td, J=22.0, 6.2Hz). 13 C NMR (101 MHz, chloroform-d) δ 152.20-150.50(m), 151.18-150.88(m), 148.81(ddd, J=133.2, 10.8, 5.8H z), 147.48, 143.25, 139.32, 138.59-137.90(m), 135.69(dt, J=246.1, 16. 1Hz), 126.44, 123.69, 123.35, 121.40, 116.39, 109.27, 107.74 (dd, J=14. 5, 3.8Hz), 106.21, 97.67(dd, J=21.2, 3.2Hz), 69.89, 34.70, 31.95, 25.62.

[0281] Example 83: Synthesis of procatalyst 37 [ka] Ligand 19 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (6.2 mg, 13.58 μmol, 1.10 equiv.) in C6D6 (0.50 mL) was added dropwise to a clear, colorless solution of thiophene (13.6 mg, 12.35 μmol, 1.00 equiv.) in anhydrous C6D6 (4.44 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.0025 M solution in C6D6. NMR analysis indicated the product was stable. The same procedure using PhMe as the solvent can be used to prepare procatalyst solutions (0.0025 M or 0.005 M) for polymerization experiments, which are used immediately after filtration.

[0282] 1 H NMR (500MHz, benzene-d6) δ 8.53(d, J=1.9Hz, 2H), 8.34(dd, J=1.8, 0.7Hz, 2H), 7.52-7.47(m, 4H), 7.45(dd, J=8.7, 0.7Hz, 2H), 7.20(d d, J=8.5, 0.6Hz, 2H), 6.92(ddd, J=8.1, 7.3, 1.6Hz, 4H), 6.89(s, 2H), 6.74-6.70(m, 2H), 6.24-6.21(m, 4H), 4.65(dd, J=10.6, 6.3Hz, 2H), 3.71(dd, J=12.8, 7.7Hz, 2H), 3.04(dd, J=11.6, 4.6Hz, 2H), 1.53(s, 18H), 1.2 6(s, 18H), 0.78(d, J=11.8Hz, 2H), 0.67(dd, J=16.2, 7.2Hz, 2H), 0.58-0.52(m, 2H), 0.52(d, J=12.0Hz, 2H). 19 F NMR (470 MHz, benzene-d6) δ -130.11 (ddd, J = 23.0, 10.5, 5.8 Hz), -131.31--131.90 (m), -160.87 (td, J = 23.0, 6.6 Hz).

[0283] Example 84: Synthesis of procatalyst 38 [ka] Ligand 19 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (5.2 mg, 9.59 μmol, 1.10 equiv.) in C6D6 (0.42 mL) was added dropwise to a clear, colorless solution of thiophene (9.6 mg, 8.72 μmol, 1.00 equiv.) in anhydrous C6D6 (3.07 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.0025 M solution in C6D6. NMR indicated the product. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.0025 M) to be used immediately after filtration in polymerization experiments.

[0284] 1 H NMR (400MHz, benzene-d6) δ 8.53(d, J=1.9Hz, 2H), 8.33(dd, J=1.8, 0.7Hz, 2H), 7.51-7.42(m, 6H), 7.16(dd, J=8.5, 0.6 Hz, 2H), 7.02-6.94(m, 6H), 6.87(s, 2H), 6.73-6.65(m, 2H), 6.36-6.30(m, 4H), 4.63(dd, J= 10.6, 6.3Hz, 2H), 3.63-3.53(m, 2H), 2.98(dd, J=11.5, 4.6Hz, 2H), 1.52(s, 18H), 1.23(s, 1 8H), 0.99(d, J=13.5Hz, 2H), 0.65-0.53(m, 2H), 0.51-0.44(m, 2H), 0.31(d, J=13.5Hz, 2H). 19 F NMR (470 MHz, benzene-d6) δ -130.09 (ddd, J = 23.0, 10.6, 6.0 Hz), -131.00--131.79 (m), -160.31 (td, J = 22.8, 6.5 Hz).

[0285] Example 85: Synthesis of bis-3,4,5-trifluoro-2-iodophenyl ether [ka] A white heterogeneous mixture of iodophenol (5.444 g, 19.870 mmol, 2.00 equiv.), K2CO3 (8.238 g, 59.610 mmol, 6.00 equiv.), and 1,4-dibromobutane (1.10 mL, 9.935 mmol, 1.00 equiv.) in acetone (100 mL) under nitrogen and equipped with a reflux condenser was placed in a heated mantle at 60 °C and stirred (500 rpm) for 36 h. After stirring, the white heterogeneous mixture was removed from the mantle. The mixture was extracted, cooled to 23 °C, diluted with CHCl (50 mL), stirred vigorously (1000 rpm) for 5 min, suction filtered through a pad of Celite, rinsed with CHCl (3 × 25 mL), and the resulting filtrate solution was concentrated onto Celite and purified by silica gel chromatography using 10% CHCl in hexanes - 50% CHCl in hexanes to give the bis-iodophenyl ether (5.086 g, mmol, 85%) as a white solid. NMR indicated the product.

[0286] 1 H NMR (500 MHz, chloroform-d) δ 6.55 (ddd, J = 11.8, 5.9, 2.3 Hz, 2H), 4.07 (h, J = 2.6 Hz, 4H), 2.15-2.07 (m, 4H). 19 F NMR (470 MHz, chloroform-d) δ −111.26 (dd, J = 23.3, 6.7 Hz), −132.95 (ddd, J = 19.9, 11.8, 6.7 Hz), −166.63-−167.33 (m). 13 C NMR (126MHz, chloroform-d) δ 153.44(m), 152.96-152.33(m), 150.64(m), 134.41(ddd, J=248.0, 17.9, 15.8Hz), 96.35(dd, J=22.0, 2.8Hz), 69.51, 25.75.

[0287] Example 86: Synthesis of 3,4,5-trifluoro-2-iodophenol [ka] A clear, colorless solution of the starting phenol (4.950 g, 33.428 mmol, 1.00 equiv), KI (9.710 g, 58.500 mmol, 1.75 equiv), and aqueous NaOH (100 mL, 100.30 mmol, 3.00 equiv, 1 N) in methanol (150 mL) and water (200 mL) under nitrogen was placed in an ice bath and vigorously stirred (1000 rpm) for 1 h, after which pre-chilled commercial aqueous bleach (84.0 mL, 58.500 mmol, 1.75 equiv, 5.2% w / w) was added dropwise over 10 min. At this point, the bright yellow solution was stirred at 0 °C for 2 h. The mixture was removed from the ice-water bath and stirred at 23 °C for 4 h. Solid NaH2PO4 (50 g) was added, followed by the addition of saturated aqueous Na2SO3 (200 mL) to reduce residual iodine. Water (100 mL) was added. The mixture was stirred vigorously for 10 min, diluted with CHCl2 (50 mL), and the biphasic yellow mixture was poured into a separatory funnel. The layers were separated, the organics were washed with aqueous Na2SO3 (2 × 100 mL), and the remaining organics were extracted from the aqueous layer using CHCl2 (2 × 25 mL). The mixture was combined, dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexanes-50% CHCl2 in hexanes to give o-iodophenol (5.444 g, 19.870 mmol, 60%) as a clear, colorless oil. NMR indicated pure product.

[0288] 1 H NMR (400 MHz, chloroform-d) δ 6.80-6.63 (m, 1H), 5.33 (s, 1H). 19 F NMR (376 MHz, chloroform-d) δ −112.07 (ddd, J = 22.3, 6.8, 2.6 Hz), −132.68 (ddd, J = 21.1, 11.1, 6.8 Hz), −166.81 (td, J = 21.7, 6.2 Hz). 13C NMR (101 MHz, chloroform-d) δ 153.58-151.73 (m), 150.78 (dd, J = 10.8, 5.5 Hz), 151.07-149.29 (m), 136.06-132.30 (m), 98.90 (ddd, J = 21.8, 3.2, 1.3 Hz), 68.51 (d, J = 26.4 Hz).

[0289] Example 87: Synthesis of Ligand 20 [ka] A mixture of thiophene boropinacolate ester (1.000 g, 1.104 mmol, 2.70 equiv., 62% pure by NMR), KPO (0.703 g, 3.312 mmol, 8.10 equiv.), Pd(AmPhos)Cl (58.0 mg, 0.0818 mmol, 0.20 equiv.), and bisphenyl iodide (0.246 g, 0.4089 mmol, 1.00 equiv.) was prepared. The mixture was evacuated and then refilled with nitrogen. This process was repeated three more times. Deoxygenated 1,4-dioxane (8.0 mL) and deoxygenated water (0.8 mL) were then added sequentially via syringe. The mixture was then placed in a heated mantle at 50 °C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was removed from the mantle, gradually cooled to 23 °C, suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the clear, black filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed using toluene (2 × 10 mL) by rotary evaporation. The black mixture was then suspended in CHCl (20 mL), suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the black filtrate was concentrated onto Celite and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 60% CHCl in hexane to give impure bisthiophene (0.202 g) as a bright yellow foam. NMR indicated the product contained impurities. This impure material was used in subsequent reactions.

[0290] To a solution of the impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (5 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 75% CHCl in hexanes to give the bisthiophene (0.141 g, 0.1280 mmol, 31% yield, 2 steps) as a white foam. NMR indicated a pure product.

[0291] 1 H NMR (500MHz, chloroform-d) δ 8.16-8.12(m, 4H), 7.43(ddd, J=8.7, 1.9, 0.9Hz, 4H), 7.38(d, J=0.9Hz, 2H), 7.35(ddd, J=10.6, 7.9, 2.1Hz, 2 H), 7.20(d, J=8.6Hz, 4H), 6.96(d, J=1.5Hz, 2H), 4.15-4.05(m, 4H), 1.91(q, J=3.2, 2.8Hz, 4H), 1.45(s, 36H). 19 F NMR (470 MHz, chloroform-d) δ −137.56 (ddd, J = 21.7, 11.4, 3.9 Hz), −147.93 (d, J = 19.3 Hz), −157.70 (td, J = 20.7, 8.1 Hz). 13 C NMR (126MHz, chloroform-d) δ 148.89-146.76(m), 147.27, 146.77-144.58(m), 143.19, 139.52(ddd, J=254.7, 16.3, 14.1Hz), 139.36, 139.25(dd, J=10.1, 3.5Hz), 127.64 , 123.67, 123.38, 123.03(dd, J=8.0, 3.0Hz), 121.41, 116.39, 111.90, 111.46-111.11(m), 109.34, 75.47(d, J=3.5Hz), 34.72, 31.98, 26.07.

[0292] Characterization of the protected ligand: 1 H NMR (500MHz, chloroform-d) δ 8.10(d, J=1.9Hz, 4H), 7.68(ddd, J=11.0, 8.3, 2.2Hz, 2H), 7.45(dd, J=8.7, 1.9Hz, 4H), 7.40(s, 2H), 7.27(d, J=8.6Hz , 4H), 4.41(s, 4H), 4.24-4.18(m, 4H), 2.94(q, J=7.1Hz, 4H), 2.13-2.02(m, 4H), 1.45(s, 36H), 0.64(t, J=7.0Hz, 6H). 19 F NMR (470MHz, chloroform-d) δ -140.52 (ddd, J=21.6, 11.5, 2.9Hz), -149.05 (d, J=19.7Hz), -157.38 (td, J=20.8, 8.4Hz).

[0293] Example 88: Synthesis of procatalyst 39 [ka] Ligand 20 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (3.4 mg, 7.39 μmol, 1.10 equiv.) in C6D6 (0.27 mL) was added dropwise to a clear, colorless solution of thiophene (7.4 mg, 6.72 μmol, 1.00 equiv.) in anhydrous C6D6 (2.42 mL). After stirring (500 rpm) for 30 min, the pale yellow solution was filtered using a 0.20 μm PTFE submicron filter to give the zirconium complex as a 0.0025 M solution in C6D6. NMR indicated the product existed as a mixture with rotamers. The complex was neutralized using d-MeOH to give the starting ligand. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.0025 M or 0.005 M) to be used immediately after filtration in the polymerization experiments.

[0294] 1H NMR (400MHz, benzene-d6) δ 8.52-8.49(m, 2H), 8.33(dd, J=1.9, 0.7Hz, 2H), 7.62(dd, J=8.6, 1.9Hz, 2H), 7.54(dd, J=8.6, 0.7Hz, 2H), 7.49(dd, J=8.7, 1.9Hz, 2H), 7.37(dd, J=8.6, 0.6Hz, 2H), 6.91-6.86(m, 2H), 6.83(s, 2H), 6.70(t , J=7.3Hz, 2H), 6.57-6.47(m, 2H), 6.17-6.13(m, 4H), 5.60-5.55(m, 2H), 4.02-3.91(m, 2H), 3.23-3. 12(m, 2H), 1.58(s, 18H), 1.29(s, 18H), 1.06(d, J=11.5Hz, 2H), 0.90-0.73(m, 2H), 0.65-0.58(m, 2H). 19 F NMR (376MHz, benzene-d6) δ -135.52 (ddd, J=22.5, 10.7, 6.3Hz), -141.09 (d, J=20.9Hz), -155.07 (td, J=21.2, 7.9Hz).

[0295] Example 89: Synthesis of procatalyst 40 [ka] Ligand 20 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (4.8 mg, 8.79 μmol, 1.10 equiv.) in C6D6 (0.38 mL) was added dropwise to a clear, colorless solution of thiophene (8.8 mg, 7.99 μmol, 1.00 equiv.) in anhydrous C6D6 (2.82 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.0025 M solution in C6D6. NMR indicated the product existed as a mixture of rotamers. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.0025 M) to be used immediately after filtration in polymerization experiments.

[0296] 1H NMR (400MHz, benzene-d6) δ 8.53(dd, J=2.0, 0.6Hz, 2H), 8.32(t, J=1.3Hz, 2H), 7.61(dd, J=8.5, 1.9Hz, 2H), 7.48-7.45(m, 2H), 7.35(dd, J=8.5, 0.6Hz, 2H), 6.98-6.93(m, 6H), 6.83(s, 2H), 6.74-6.66(m, 2H), 6.57-6.49 (m, 2H), 6.25-6.19(m, 4H), 6.08-5.98(m, 2H), 4.00-3.91(m, 2H), 3.20-3.11(m, 2H), 1.58(s, 1 8H), 1.32-1.27(m, 2H), 1.28(s, 18H), 0.83-0.76(m, 2H), 0.76-0.68(m, 2H), 0.58-0.46(m, 2H). 19 F NMR (376MHz, benzene-d6) δ -134.93 (ddd, J=22.5, 10.5, 6.5Hz), -140.74 (d, J=19.9Hz), -154.84 (td, J=21.4, 7.9Hz).

[0297] Example 90: Synthesis of bis-4,5,6-trifluoro-2-iodophenyl ether [ka] A white heterogeneous mixture of iodophenol (1.550 g, 5.657 mmol, 2.00 equiv.), KCO (2.346 g, 16.972 mmol, 6.00 equiv.), and 1,4-dibromobutane (0.34 mL, 2.829 mmol, 1.00 equiv.) in acetone (50 mL) under nitrogen and equipped with a reflux condenser was placed in a heated mantle at 60 °C and stirred (500 rpm) for 36 h. After stirring, the white heterogeneous mixture was removed from the mantle and stirred. Cool to 23 °C, dilute with CHCl (50 mL), stir vigorously (1000 rpm) for 5 min, suction filter through a Celite pad, rinse with CHCl (3 × 25 mL), concentrate the resulting filtrate solution onto Celite, and purify by silica gel chromatography using 10% CHCl in hexanes - 50% CHCl in hexanes to give the bis-iodophenyl ether (1.410 g, 2.342 mmol, 83%) as a white solid. NMR indicated the product.

[0298] 1 H NMR (400MHz, chloroform-d) δ 7.38 (td, J=8.5, 2.6Hz, 2H), 4.20-4.09 (m, 4H), 2.09 (h, J=2.7Hz, 4H). 19 F NMR (376 MHz, chloroform-d) δ −138.88 (ddd, J = 20.5, 9.0, 3.2 Hz), −146.39 (dt, J = 19.7, 2.8 Hz), −155.64 (td, J = 20.0, 7.9 Hz). 13 C NMR (126MHz, chloroform-d) δ 147.31(ddd, J=250.6, 10.6, 2.7Hz), 144.51(dd, J=10.0, 3.9Hz), 144.51(ddd, J=254.7, 11.0, 4.1Hz), 140.78( ddd, J=254.1, 16.0, 14.1Hz), 120.35(dd, J=20.2, 3.7Hz), 82.83(dd, J=7.7, 4.2Hz), 74.23(d, J=4.5Hz), 26.72.

[0299] Example 91: Synthesis of 4,5,6-trifluoro-2-iodophenyl ether [ka] A clear, colorless solution of the starting phenol (4.700 g, 31.740 mmol, 1.00 equiv), KI (9.221 g, 55.544 mmol, 1.75 equiv), and aqueous NaOH (95.2 mL, 95.208 mmol, 3.00 equiv, 1N) in methanol (200 mL) and water (100 mL) under nitrogen was placed in an ice bath and vigorously stirred (1000 rpm) for 1 h, after which pre-chilled commercial aqueous bleach (80.0 mL, 55.544 mmol, 1.75 equiv, 5.2% w / w) was added dropwise over 10 min. At this point, the bright yellow solution was stirred at 0 °C for 2 h. The mixture was removed from the ice-water bath and stirred at 23 °C for 4 h. Solid KH2PO4 (25 g) was added, followed by the addition of saturated aqueous Na2SO3 (100 mL) to reduce residual iodine. Water (100 mL) was added. The mixture was stirred vigorously for 10 min, diluted with CHCl2 (50 mL), and the biphasic yellow mixture was poured into a separatory funnel. The layers were separated, the organics were washed with aqueous Na2SO3 (2 × 50 mL), and the remaining organics were extracted from the aqueous layer using CHCl2 (2 × 25 mL). The mixture was combined, dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexanes-50% CHCl2 in hexanes to give o-iodophenol (4.202 g, 15.337 mmol, 48%) as a clear, pale yellow oil. NMR indicated pure product.

[0300] 1 H NMR (400 MHz, chloroform-d) δ 7.33 (tdd, J = 8.8, 2.7, 0.9 Hz, 1H), 5.37 (s, 1H). 19 F NMR (376 MHz, chloroform-d) δ −143.20 (ddd, J = 21.0, 9.5, 3.8 Hz), −152.54 (dt, J = 19.4, 3.4 Hz), −156.04 (td, J = 20.0, 7.6 Hz). 13C NMR (101 MHz, chloroform-d) δ 145.31 (ddd, J = 247.4, 10.7, 2.4 Hz), 142.06-141.31 (m), 139.45 (ddd, J = 249.4, 12.7, 3.8 Hz), 139.64-139.11 (m), 119.82 (dd, J = 20.6, 4.1 Hz), 75.21 (dd, J = 8.0, 4.6 Hz).

[0301] Example 92: Synthesis of Ligand 21 [ka] A mixture of thiophene boropinacolate ester (1.000 g, 1.104 mmol, 2.70 equiv., 62% pure by NMR), KPO (0.703 g, 3.312 mmol, 8.10 equiv.), Pd(AmPhos)Cl (58.0 mg, 0.0818 mmol, 0.20 equiv.), and bisphenyl iodide (0.230 g, 0.4089 mmol, 1.00 equiv.) was prepared. The mixture was evacuated and then refilled with nitrogen. This process was repeated three more times. Deoxygenated 1,4-dioxane (8.0 mL) and deoxygenated water (0.8 mL) were then added sequentially via syringe. The mixture was then placed in a heated mantle at 50 °C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was removed from the mantle, gradually cooled to 23 °C, suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the clear, black filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed using toluene (2 × 10 mL) by rotary evaporation. The black mixture was then suspended in CHCl (20 mL), suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the black filtrate was concentrated onto Celite and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 75% CHCl in hexane to give impure bisthiophene (0.232 g) as a pale red, amorphous foam. NMR indicated the product contained impurities. This impure material was used in subsequent reactions.

[0302] To a solution of the impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (5 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 75% CHCl in hexanes to give the bisthiophene (0.143 g, 0.1346 mmol, 33% yield, 2 steps) as a white foam. NMR indicated a pure product.

[0303] 1 H NMR (500MHz, chloroform-d) δ 8.15(dd, J=1.9, 0.6Hz, 4H), 7.66(d, J=2.6Hz, 2H), 7.42(dd, J=8.6, 1.9Hz, 4H), 7.35(s, 2H), 7.24-7.20(m, 4H), 7.18(dd, J =8.7, 2.6Hz, 2H), 7.04(s, 2H), 6.79(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). 13 C NMR (126 MHz, chloroform-d) δ 152.34, 146.98, 142.94, 139.54, 129.92, 128.19, 127.84, 127.46, 124.63, 123.58, 123.27, 120.85, 116.30, 115.08, 113.72, 109.51, 70.29, 34.74, 32.05, 25.81.

[0304] Example 93: Synthesis of procatalyst 41 [ka] Ligand 21 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (4.3 mg, 9.53 μmol, 1.10 equiv.) in C6D6 (0.18 mL) was added dropwise to a clear, colorless solution of thiophene (9.2 mg, 8.66 μmol, 1.00 equiv.) in anhydrous C6D6 (1.55 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.005 M solution in C6D6. NMR analysis indicated the product was stable. The same procedure using PhMe as the solvent can be used to prepare procatalyst solutions (0.0025 M or 0.005 M) for polymerization experiments, which are used immediately after filtration.

[0305] 1 H NMR (500MHz, benzene-d6) δ 8.43(dd, J=2.0, 0.6Hz, 2H), 8.29(dd, J=1.9, 0.6Hz, 2H), 7.53-7.48(m, 4H), 7.45(dd, J=8.5, 1.9Hz, 2H), 7.34(dd, J=8.7, 0.6Hz, 2H), 7.31(d, J=2.6Hz, 2H), 7.22-7.19(m, 2H), 6.91-6.86(m, 2H), 6.83(dd, J=8.7, 2.7Hz, 2H), 6.81(s , 2H), 6.79-6.74(m, 2H), 6.24-6.19(m, 4H), 4.98(d, J=8.7Hz, 2H), 3.88-3.78(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). 13C NMR (126 MHz, benzene-d6) δ 154.32, 152.71, 146.13, 143.43, 143.02, 139.29, 139.12, 131.33, 130.56, 130.43, 129.56, 128.90, 128.33, 126.54, 126.07, 125.16, 124.69, 124.51, 124.12, 122.73, 122.43, 121.25, 118.17, 116.44, 115.69, 115.54, 112.22, 108.73, 74.66, 72.01, 34.54, 34.46, 31.94, 31.71, 25.77.

[0306] Example 94: Synthesis of procatalyst 42 [ka] Ligand 21 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (3.8 mg, 7.04 μmol, 1.10 equiv.) in C6D6 (0.16 mL) was added dropwise to a clear, colorless solution of thiophene (6.8 mg, 6.40 μmol, 1.00 equiv.) in anhydrous C6D6 (1.12 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.005 M solution in C6D6. NMR analysis indicated the product was stable. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M) to be used immediately after filtration in polymerization experiments.

[0307] 1H NMR (400MHz, ベンゼン-d6) δ 8.43 (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, 2.7Hz, 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), 3.19-3. 06 (m, 2H), 1.43 (s, 18H), 1.28 (s, 18H), 0.89 (d, J=13.4Hz, 2H), 0.70-0.57 (m, 2H), 0.47-0.36 (m, 2H), 0.27-0.20 (m, 2H). 13 C NMR (101MHz, ベンゼン-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.

[0308] Example 95: Synthesis of ビス-4-クロロ-2-ヨードフェニルエーテルの

change

[0309] 1 H NMR (500MHz, chloroform-d) δ 7.73(d, J=2.5Hz, 2H), 7.27-7.23(m, 2H), 6.73(d, J=8.8Hz, 2H), 4.14-4.04(m, 4H), 2.10(h, J=2.4Hz, 4H). 13 C NMR (126 MHz, chloroform-d) δ 156.29, 138.50, 129.17, 126.28, 112.40, 86.72, 69.01, 25.92.

[0310] Example 96: Synthesis of Ligand 22 [ka] A mixture of thiophene boropinacolate ester (1.000 g, 1.104 mmol, 2.70 equiv., 62% pure by NMR), KPO (0.703 g, 3.312 mmol, 8.10 equiv.), Pd(AmPhos)Cl (58.0 mg, 0.0818 mmol, 0.20 equiv.), and bisphenyl iodide (0.230 g, 0.4089 mmol, 1.00 equiv.) was prepared. The mixture was evacuated and then refilled with nitrogen. This process was repeated three more times. Deoxygenated 1,4-dioxane (8.0 mL) and deoxygenated water (0.8 mL) were then added sequentially via syringe. The mixture was then placed in a heated mantle at 50 °C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was removed from the mantle, gradually cooled to 23 °C, suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the clear, black filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed using toluene (2 × 10 mL) by rotary evaporation. The black mixture was then suspended in CHCl (20 mL), suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the black filtrate was concentrated onto Celite and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 75% CHCl in hexane to give impure bisthiophene (0.161 g) as a pale red, amorphous foam. NMR indicated the product contained impurities. This impure material was used in subsequent reactions.

[0311] To a solution of the impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (5 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 75% CHCl in hexanes to give the bisthiophene (0.121 g, 0.1139 mmol, 24% yield, 2 steps) as a white solid. NMR indicated a pure product.

[0312] 1 H NMR (500MHz, chloroform-d) δ 8.13(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=8.6Hz, 4H), 7.1 0(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 C NMR (126 MHz, chloroform-d) δ 154.27, 146.45, 142.91, 139.52, 133.98, 131.08, 127.26, 123.54, 123.24, 122.78, 121.45, 120.37, 116.29, 114.09, 114.02, 109.48, 69.93, 34.70, 32.01, 25.84.

[0313] Example 97: Synthesis of procatalyst 43 [ka] Ligand 22 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (5.0 mg, 11.10 μmol, 1.10 equiv.) in C6D6 (0.20 mL) was added dropwise to a clear, colorless solution of thiophene (10.7 mg, 10.10 μmol, 1.00 equiv.) in anhydrous C6D6 (1.82 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.005 M solution in C6D6. NMR indicated the product existed as a mixture of rotamers. The same procedure using PhMe as the solvent can be used to prepare procatalyst solutions (0.0025 M or 0.005 M) for polymerization experiments, which were used immediately after filtration.

[0314] 1 H NMR (500MHz, benzene-d6) δ 8.51-8.44(m, 4H), 8.35-8.26(m, 2H), 7.63-7.54(m, 4H), 7.29-7.26(m, 2H), 7.14(d, J=8.3H z, 2H), 6.94(s, 2H), 6.91(dd, J=8.3, 2.1Hz, 2H), 6.85-6.77(m, 4H), 6.51-6.48(m, 4H), 6.40 -6.32(m, 2H), 5.86(d, J=2.1Hz, 2H), 3.48-3.38(m, 2H), 3.32(m, 2H), 1.73(d, J=13.1Hz, 2H) , 1.33(s, 18H), 1.23(s, 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.

[0315] Example 98: Synthesis of procatalyst 44 [ka] Ligand 22 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (6.8 mg, 12.43 μmol, 1.10 equiv.) in C6D6 (0.27 mL) was added dropwise to a clear, colorless solution of thiophene (12.0 mg, 11.30 μmol, 1.00 equiv.) in anhydrous C6D6 (1.99 mL). After stirring (500 rpm) for 30 min, the pale yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.005 M solution in C6D6. NMR indicated the product existed as a mixture of rotamers. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M) to be used immediately after filtration in polymerization experiments.

[0316] 1 H NMR (400MHz, benzene-d6) δ 8.57(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(ddq, 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).

[0317] Example 99: Synthesis of bis-5-chloro-2-iodophenyl ether [ka] 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) under nitrogen and equipped with a reflux condenser was placed in a heated mantle at 60 °C and stirred (500 rpm) for 36 h. After stirring, the white heterogeneous mixture was removed from the mantle. The mixture was cooled to 23 °C, diluted with CHCl (50 mL), stirred vigorously (1000 rpm) for 5 min, suction filtered through a Celite pad, rinsed with CHCl (3 × 25 mL), and the resulting filtrate solution was concentrated onto Celite and purified by silica gel chromatography using 10% CHCl in hexanes - 50% CHCl in hexanes to give the bis-iodophenyl ether (2.456 g, 4.362 mmol, 90%) as a white solid. NMR indicated the product.

[0318] 1 H NMR (400MHz, chloroform-d) δ 7.64(d, J=8.3Hz, 2H), 6.79(d, J=2.2Hz, 2H), 6.70(dd, J=8.3, 2.2Hz, 2H), 4.16-4.03(m, 4H), 2.15-2.04(m, 4H). 13 C NMR (101 MHz, chloroform-d) δ 158.00, 139.68, 135.13, 122.49, 112.66, 83.83, 68.90, 25.86.

[0319] Example 100: Synthesis of Ligand 23 [ka] A mixture of thiophene boropinacolate ester (1.000 g, 1.104 mmol, 2.70 equiv., 62% pure by NMR), KPO (0.703 g, 3.312 mmol, 8.10 equiv.), Pd(AmPhos)Cl (58.0 mg, 0.0818 mmol, 0.20 equiv.), and bisphenyl iodide (0.258 g, 0.4089 mmol, 1.00 equiv.) was prepared. The mixture was evacuated and then refilled with nitrogen. This process was repeated three more times. Deoxygenated 1,4-dioxane (8.0 mL) and deoxygenated water (0.8 mL) were then added sequentially via syringe. The mixture was then placed in a heated mantle at 50 °C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was removed from the mantle, gradually cooled to 23 °C, suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the clear, black filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed using toluene (2 × 10 mL) by rotary evaporation. The black mixture was then suspended in CHCl (20 mL), suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the black filtrate was concentrated onto Celite and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 100% CHCl in hexane to give impure bisthiophene (0.271 g) as a pale red, amorphous foam. NMR indicated the product contained impurities. This impure material was used in subsequent reactions.

[0320] To a solution of the impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (5 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 25% to 100% CHCl in hexanes to give the bisthiophene (0.126 g, 0.1114 mmol, 27% yield, two steps) as a white solid. NMR indicated a pure product.

[0321] 1 H NMR (500MHz, chloroform-d) δ 8.13(d, J=1.9Hz, 4H), 7.41(h, J=8.6, 7.4Hz, 4H), 7.37(s, 2H), 7.27(d, J=9.4Hz, 2H), 7.22(d, J=8 .6Hz, 4H), 6.64(d, J=9.0Hz, 2H), 4.84(s, 2H), 3.95-3.85(m, 4H), 1.81-1.73(m, 4H), 1.44(s, 36H). 13 C NMR (126 MHz, chloroform-d) δ 156.55, 146.38, 143.30, 139.26, 134.56, 130.70, 125.87, 125.62, 123.84, 123.40, 122.00, 120.38, 116.38, 111.87, 111.71, 109.32, 69.13, 34.74, 32.00, 25.74.

[0322] Example 101: Synthesis of procatalyst 45 [ka] Ligand 23 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (4.6 mg, 10.02 μmol, 1.10 equiv.) in C6D6 (0.18 mL) was added dropwise to a clear, colorless solution of thiophene (10.3 mg, 9.11 μmol, 1.00 equiv.) in anhydrous C6D6 (1.64 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.005 M solution in C6D6. NMR indicated the product existed as a mixture of rotamers. The same procedure using PhMe as the solvent can be used to prepare procatalyst solutions (0.0025 M or 0.005 M) to be used immediately after filtration in polymerization experiments.

[0323] 1 H NMR (500MHz, benzene-d6) δ 8.42(d, J=1.9Hz, 2H), 8.26(d, J=1.9Hz, 2H), 7.47(ddd, J=8.5, 6.3, 1.9Hz, 2H), 7.38(d, J=8.7Hz, 2H), 7 .25(d, J=8.5Hz, 2H), 6.99-6.95(m, 6H), 6.94(s, 2H), 6.86(d, J=8.8Hz, 2H), 6.80(d, J=7.4Hz, 2H), 6.37 -6.32(m, 2H), 6.09(m, 2H), 4.91(d, J=8.8Hz, 2H), 3.79(t, J=10.1Hz, 2H), 3.20-3.13(m, 2H), 1.47(s, 18 H), 1.27(s, 18H), 0.95-0.78(m, 2H), 0.73(d, J=11.6Hz, 2H), 0.63-0.55(m, 2H), 0.35(d, J=11.7Hz, 2H).

[0324] Example 102: Synthesis of procatalyst 46 [ka] Ligand 23 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (4.0 mg, 7.40 μmol, 1.10 equiv.) in C6D6 (0.16 mL) was added dropwise to a clear, colorless solution of thiophene (7.6 mg, 6.72 μmol, 1.00 equiv.) in anhydrous C6D6 (1.18 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.005 M solution in C6D6. NMR indicated the product existed as a complex rotamer mixture. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M) to be used immediately after filtration in polymerization experiments.

[0325] Example 103: Synthesis of bis-3,4-dichloro-2-iodophenyl ether [ka] A white heterogeneous mixture of iodophenol (4.112 g, 14.234 mmol, 2.20 equiv.), K2CO3 (5.902 g, 42.702 mmol, 6.60 equiv.), and 1,4-dibromobutane (0.77 mL, 6.470 mmol, 1.00 equiv.) in acetone (65 mL) under nitrogen and equipped with a reflux condenser was placed in a heated mantle at 60 °C and stirred (500 rpm) for 36 h. After that, the white heterogeneous mixture was removed from the mantle, cooled to 23 °C, diluted with aqueous NaOH (100 mL, 1 N), stirred for 2 min, and vacuumed. The filtered white solid was rinsed with aqueous NaOH (2 × 25 mL, 1 N), then with water (2 × 25 mL) and cold CHCl (2 × 20 mL). The resulting filtered white solid was collected, and the biphasic mixture was poured into a separatory funnel. The layers were separated, the organics were washed with aqueous NaOH (2 × 25 mL), and the remaining organics were extracted with CHCl (2 × 25 mL), combined, dried over solid NaSO, concentrated, and combined with the filtered solid to give the iodophenyl ether (3.813 g, 6.034 mmol, 93%) as a white solid. NMR (at 60 °C and 100 °C) indicated the product.

[0326] VT NMR at 60°C: 1 H NMR (400MHz, chloroform-d) δ 7.38 (d, J=8.8Hz, 2H), 6.65 (d, J=8.9Hz, 2H), 4.11 (q, J=4.3, 3.2Hz, 4H), 2.11 (dt, J=5.4, 3.3Hz, 4H).

[0327] VT NMR at 100°C: 1 H NMR (400MHz, DMSO-d6) δ 7.54 (dd, J=8.9, 1.5Hz, 2H), 6.96 (dd, J=8.9, 1.8Hz, 2H), 4.16 (ddt, J=5.9, 3.6, 2.2Hz, 4H), 1.97 (dq, J=5.9, 2.6Hz, 4H). 13 C NMR (101MHz, DMSO-d6) δ 158.69, 136.57, 130.92, 130.75, 123.17, 93.97, 70.20, 25.87.

[0328] Example 104: Synthesis of bis-4,5-dichloro-2-iodophenyl ether [ka] A white heterogeneous mixture of iodophenol (2.454 g, 8.494 mmol, 2.00 equiv.), K2CO3 (3.522 g, 25.483 mmol, 6.00 equiv.), and 1,4-dibromobutane (0.50 mL, 4.247 mmol, 1.00 equiv.) in acetone (50 mL) under nitrogen and equipped with a reflux condenser was placed in a heated mantle at 60 °C and stirred (500 rpm) for 36 h. After that, the white heterogeneous mixture was removed from the mantle, cooled to 23 °C, diluted with aqueous NaOH (100 mL, 1 N), stirred for 2 min, and vacuumed. The filtered white solid was rinsed with aqueous NaOH (2 × 25 mL, 1 N), then with water (2 × 25 mL) and cold CHCl (2 × 20 mL). The resulting filtered white solid was collected, and the biphasic mixture of filtrate was poured into a separatory funnel. The layers were separated, the organics were washed with aqueous NaOH (2 × 25 mL), and the remaining organics were extracted with CHCl (2 × 25 mL), combined, dried over solid NaSO, concentrated, and combined with the filtered solid to give the iodophenyl ether (2.272 g, 3.596 mmol, 85%) as a white solid. NMR (at 55 °C) indicated the product.

[0329] The NMR spectrum was obtained at 55°C: 1 H NMR (500 MHz, chloroform-d) δ 7.80 (s, 2H), 6.88 (s, 2H), 4.12 (qd, J = 5.6, 3.7, 3.3 Hz, 4H), 2.11 (dq, J = 5.7, 2.9 Hz, 4H). 13 C NMR (126 MHz, chloroform-d) δ 156.81, 139.43, 133.07, 125.07, 113.61, 84.17, 69.50, 25.82.

[0330] Example 105: Synthesis of 4,5-dichloro-2-iodophenol and 3,4-dichloro-2-iodophenol [ka] A clear, colorless solution of the starting phenol (5.020 g, 30.798 mmol, 1.00 equiv), KI (8.947 g, 53.896 mmol, 1.75 equiv), and aqueous NaOH (92 mL, 92.394 mmol, 3.00 equiv, 1N) in methanol (250 mL) and water (125 mL) under nitrogen was placed in an ice bath and vigorously stirred (1000 rpm) for 1 h, after which pre-chilled commercial aqueous bleach (77 mL, 53.896 mmol, 1.75 equiv, 5.2% w / w) was added dropwise over 10 min. At this point, the bright yellow solution was stirred at 0 °C for 2 h, the mixture was removed from the ice-water bath and stirred at 23 °C for 4 h, solid KH 2 PO 4 (25 g) was added, followed by the addition of saturated aqueous Na 2 SO 3 (100 mL) to reduce residual iodine, water (100 mL), the mixture was stirred vigorously for 10 min, diluted with CHCl 2 (50 mL), the biphasic yellow mixture was poured into a separatory funnel, the layers were separated, and the organics were washed with aqueous Na 2 SO 3 (2 × 50 mL), and the remaining organics were washed with CHCl 2 (2 The aqueous layer was extracted with 10 mL of HCl (3×25 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexane-50% CHCl in hexane to give 2-iodo-4,5-dichlorophenol (2.738 g, 9.478 mmol, 31%) as a clear, pale yellow amorphous foam and 2-iodo-3,4-dichlorophenol (3.325 g, 11.509 mmol, 37%) as a clear, pale yellow foam. NMR indicated pure product.

[0331] Characterization of 2-iodo-4,5-dichlorophenol: 1 H NMR (500 MHz, chloroform-d) δ 7.71 (s, 1H), 7.10 (s, 1H), 5.27 (s, 1H).

[0332] Characterization of 2-iodo-3,4-dichlorophenol: 1 H NMR (400 MHz, chloroform-d) δ 7.32 (d, J = 8.9 Hz, 1H), 6.86 (d, J = 8.8 Hz, 1H), 5.44 (s, 1H). 13C NMR (101 MHz, chloroform-d) δ 155.15, 136.20, 130.76, 123.74, 113.74, 91.99.

[0333] Example 106: Synthesis of Ligand 24 [ka] A mixture of thiophene boropinacolate ester (1.000 g, 1.104 mmol, 2.70 equiv., 62% pure by NMR), KPO (0.703 g, 3.312 mmol, 8.10 equiv.), Pd(AmPhos)Cl (58.0 mg, 0.0818 mmol, 0.20 equiv.), and bisphenyl iodide (0.258 g, 0.4089 mmol, 1.00 equiv.) was prepared. The mixture was evacuated and then refilled with nitrogen. This process was repeated three more times. Deoxygenated 1,4-dioxane (8.0 mL) and deoxygenated water (0.8 mL) were then added sequentially via syringe. The mixture was then placed in a heated mantle at 50 °C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was removed from the mantle, gradually cooled to 23 °C, suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the clear, black filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed using toluene (2 × 10 mL) by rotary evaporation. The black mixture was then suspended in CHCl (20 mL), suction filtered onto a pad of silica gel, rinsed with CHCl (4 × 20 mL), and the black filtrate was concentrated onto Celite and purified by silica gel chromatography via an ISCO chromatographic purification system using 10% to 100% CHCl in hexane to give impure bisthiophene (0.212 g) as a pale red, amorphous foam. NMR indicated the product contained impurities. This impure material was used in subsequent reactions.

[0334] To a solution of the impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (5 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 25% to 100% CHCl in hexanes to give the bisthiophene (0.113 g, 0.0999 mmol, 24% yield, 2 steps) as a white solid. NMR indicated a pure product.

[0335] 1 H NMR (500MHz, chloroform-d) δ 8.13(d, J=1.9Hz, 4H), 7.85(s, 2H), 7.40(dd, J=8.6, 1.9Hz, 4H), 7.32(s, 2H), 7.18(d, J=8 .6Hz, 4H), 7.03(s, 2H), 6.46(s, 2H), 4.11-4.05(m, 4H), 2.04-1.96(m, 4H), 1.44(s, 36H). 13 C NMR (126 MHz, chloroform-d) δ 152.71, 146.95, 143.16, 139.40, 131.51, 130.92, 127.07, 125.84, 123.68, 123.34, 122.96, 120.92, 116.36, 115.20, 112.57, 109.39, 70.17, 34.72, 32.00, 25.85.

[0336] Example 107: Synthesis of procatalyst 47 [ka] Ligand 24 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (3.9 mg, 8.56 μmol, 1.10 equiv.) in C6D6 (0.16 mL) was added dropwise to a clear, colorless solution of thiophene (8.8 mg, 7.78 μmol, 1.00 equiv.) in anhydrous C6D6 (1.40 mL). After stirring (500 rpm) for 30 min, the pale yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.005 M solution in C6D6. NMR indicated the product existed as a mixture of rotamers. The same procedure using PhMe as the solvent can be used to prepare procatalyst solutions (0.0025 M or 0.005 M) to be used immediately after filtration in polymerization experiments.

[0337] 1 H NMR (500MHz, benzene-d6) δ 8.54(dd, J=1.9, 0.7Hz, 2H), 8.42(dd, J=1.8, 0.8Hz, 2H), 7.62-7.56(m, 4H), 7.47(d d, J=8.6, 1.9Hz, 2H), 7.18(dd, J=8.5, 0.7Hz, 2H), 6.99-6.96(m, 6H), 6.94-6.90(m, 2H), 6.77(s, 2H), 6.38-6.32(m, 4H), 5.58(s, 2H), 3.58-3.50(m, 2H), 2.85-2.79(m, 2H), 1.48(s, 18H), 1.30(s, 18H), 0.92-0.83(m, 2H), 0.72(d, 2H), 0.59-0.54(m, 4H).

[0338] Example 108: Synthesis of procatalyst 48 [ka] Ligand 24 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (4.2 mg, 7.78 μmol, 1.10 equiv.) in C6D6 (0.17 mL) was added dropwise to a clear, colorless solution of thiophene (8.0 mg, 7.07 μmol, 1.00 equiv.) in anhydrous C6D6 (1.24 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.005 M solution in C6D6. NMR indicated the product existed as a mixture of rotamers. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M) to be used immediately after filtration in polymerization experiments.

[0339] 1 H NMR (500MHz, benzene-d6) δ 8.56(dd, J=2.0, 0.6Hz, 2H), 8.44(dd, J=1.7, 0.8Hz, 2H), 7.62-7.53(m, 4H), 7.46(dd, J=8.6, 1.9Hz, 2H), 7.16-7.13(m, 2H), 6.99-6.84(m, 4H), 6.77(s, 2H), 6.52-6.47(m, 6H) ), 6.42(dd, J=8.1, 1.3Hz, 2H), 5.60(s, 2H), 3.55-3.45(m, 2H), 2.83-2.77(m, 2H), 1.4 8(s, 18H), 1.30(s, 18H), 1.06-0.98(m, 2H), 0.55-0.48(m, 4H), 0.45(d, J=13.7Hz, 2H).

[0340] Example 109: Synthesis of Ligand 25 [ka] A mixture of thiophene boropinacolate ester (2.017 g, 2.586 mmol, 3.00 equiv., 72% pure by NMR), KPO (1.647 g, 7.758 mmol, 9.00 equiv.), Pd(AmPhos)Cl (122.0 mg, 0.1724 mmol, 0.20 equiv.), and bisphenyl iodide (0.604 g, 0.8620 mmol, 1.00 equiv.) was prepared. The mixture was evacuated and then refilled with nitrogen. This process was repeated three more times. Deoxygenated 1,4-dioxane (17.0 mL) and deoxygenated water (1.7 mL) were then added sequentially via syringe. The mixture was then placed in a heated mantle at 50 °C. After 40 hours of vigorous stirring (1000 rpm), the black mixture was removed from the mantle, gradually cooled to 23 °C, suction filtered onto a silica gel pad, rinsed with CHCl (4 × 20 mL), and the clear, black filtrate was concentrated. Residual 1,4-dioxane was azeotropically removed using toluene (2 × 10 mL) by rotary evaporation. The black mixture was then suspended in CHCl (20 mL), suction filtered onto a silica gel pad, rinsed with CHCl (4 × 20 mL), and the black filtrate was concentrated onto Celite. The bisthiophene (0.162 g) was purified by silica gel chromatography via an ISCO chromatography purification system with 10% to 50% CHCl in hexanes to give the bisthiophene (0.162 g) as a red, amorphous oil. NMR indicated the product existed as a mixture of rotamers and contained a small amount of impurities. This material was used in the next reaction without further purification.

[0341] To a solution of the impure coupled product in CHCl-1,4-dioxane (10 mL, 1:1) under nitrogen at 23 °C, concentrated HCl (5 mL) was added. The amber solution was stirred (500 rpm) for 20 h, diluted with 1 N HCl (10 mL) and CHCl (10 mL), poured into a separatory funnel, separated, and the organics were washed with 1 N HCl (1 × 10 mL). The remaining organics were extracted from the aqueous solution using CHCl (2 × 10 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography via an ISCO chromatographic purification system with 10% to 75% CHCl in hexanes to give the bisthiophene (0.115 g, 0.09583 mmol, 11% yield, two steps) as a light tan solid. NMR indicated a pure product.

[0342] 1 H NMR (500MHz, chloroform-d) δ 8.13(d, J=1.9Hz, 4H), 7.44-7.38(m, 4H), 7.39(s, 2H), 7.21(d, J=8.6Hz , 4H), 6.98(s, 2H), 3.96-3.91(m, 4H), 1.85-1.80(m, 4H), 1.44(s, 36H). 13 C NMR (126 MHz, chloroform-d) δ 156.24, 146.49, 143.49, 139.20, 136.25, 134.68, 125.81, 124.47, 123.91, 123.49, 120.80, 120.64, 116.49, 112.77, 110.93, 109.20, 69.04, 34.75, 31.98, 25.60.

[0343] Example 110: Synthesis of procatalyst 49 [ka] Ligand 25 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of ZrBn4 (4.3 mg, 9.35 μmol, 1.10 equiv.) in C6D6 (0.17 mL) was added dropwise to a clear, colorless solution of thiophene (10.2 mg, 8.50 μmol, 1.00 equiv.) in anhydrous C6D6 (1.53 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the zirconium complex as a 0.005 M solution in C6D6. NMR indicated the product existed as a mixture of rotamers. The same procedure using PhMe as the solvent can be used to prepare procatalyst solutions (0.0025 M or 0.005 M) to be used immediately after filtration in polymerization experiments.

[0344] 1 H NMR (400MHz, benzene-d6) δ 8.48(d, J=1.9Hz, 2H), 8.36(d, J=1.8Hz, 2H), 7.59(d, J=8.7Hz, 2H), 7.50(ddd, J=8.8 , 3.8, 1.9Hz, 4H), 7.23(d, J=8.6Hz, 2H), 6.98-6.94(m, 4H), 6.89(s, 2H), 6.74(t, J=7. 3Hz, 2H), 6.27-6.21(m, 4H), 5.41(s, 2H), 3.60-3.50(m, 2H), 2.97-2.90(m, 2H), 1.49 (s, 18H), 1.28(s, 18H), 1.16(d, J=13.9Hz, 2H), 0.90-0.80(m, 2H), 0.68-0.60(m, 2H).

[0345] Example 111: Synthesis of procatalyst 50 [ka] Ligand 25 was azeotropically dried using PhMe (4 x 10 mL) prior to use. In a nitrogen-filled glovebox at 23 °C, a solution of HfBn4 (4.0 mg, 7.33 μmol, 1.10 equiv.) in C6D6 (0.16 mL) was added dropwise to a clear, colorless solution of thiophene (8.0 mg, 6.67 μmol, 1.00 equiv.) in anhydrous C6D6 (1.17 mL). After stirring (500 rpm) for 30 min, the pale bright yellow solution was filtered using a 0.20 μm PTFE submicron filter to obtain the hafnium complex as a 0.005 M solution in C6D6. NMR indicated the product existed as a mixture of rotamers. The same procedure using PhMe as the solvent can be used to prepare the procatalyst solution (0.005 M) to be used immediately after filtration in polymerization experiments.

[0346] 1 H NMR (400MHz, benzene-d6) δ 8.51(d, J=1.9Hz, 2H), 8.39(d, J=1.8Hz, 2H), 7.61(d, J=9.0Hz, 2H), 7.50(ddd, J=21.9, 8.7 , 1.9Hz, 4H), 7.19(d, J=8.6Hz, 2H), 6.98-6.94(m, 4H), 6.90(s, 2H), 6.75(t, J=7.5Hz, 2H), 6 .41-6.36(m, 4H), 5.31(s, 2H), 3.43-3.35(m, 2H), 2.87-2.79(m, 2H), 1.49(s, 18H), 1.29(s, 18H), 1.06(d, J=14.1Hz, 2H), 0.95-0.82(m, 2H), 0.59-0.48(m, 2H), 0.41(d, J=14.0Hz, 2H).

[0347] Example 112: Synthesis of bis-3,4,5-trichloro-2-iodophenyl ether [ka] A white heterogeneous mixture of iodophenol (1.315 g, 4.067 mmol, 2.00 equiv.), K2CO3 (1.686 g, 12.201 mmol, 6.00 equiv.), and 1,4-dibromobutane (0.24 mL, 2.034 mmol, 1.00 equiv.) in acetone (50 mL) under nitrogen and equipped with a reflux condenser was placed in a heated mantle at 60 °C and stirred (500 rpm) for 36 h. After that, the white heterogeneous mixture was removed from the mantle, cooled to 23 °C, diluted with aqueous NaOH (100 mL, 1 N), stirred for 2 min, and vacuumed. The filtered white solid was rinsed with aqueous NaOH (2 × 25 mL, 1 N), then with water (2 × 25 mL) and cold CHCl (2 × 20 mL). The resulting filtered white solid was collected, and the biphasic mixture of filtrate was poured into a separatory funnel. The layers were separated, the organics were washed with aqueous NaOH (2 × 25 mL), and the remaining organics were extracted with CHCl (2 × 25 mL), combined, dried over solid NaSO, concentrated, and combined with the filtered solid to give the iodophenyl ether (1.300 g, 1.855 mmol, 91%) as a white solid. NMR (at 60 °C) indicated the product.

[0348] NMR spectra were obtained at 60°C: 1 H NMR (500 MHz, chloroform-d) δ 6.87 (s, 2H), 4.21-4.08 (m, 4H), 2.13 (dq, J = 5.3, 3.4, 2.7 Hz, 4H). 13 C NMR (126 MHz, chloroform-d) δ 157.26, 139.11, 134.26, 123.39, 111.64, 91.01, 69.80, 25.82.

[0349] Example 113: Synthesis of 3,4,5-trichlorophenol-2-iodophenol [ka] A clear, colorless solution of the starting phenol (3.600 g, 18.233 mmol, 1.00 equiv), KI (5.297 g, 31.909 mmol, 1.75 equiv), and aqueous NaOH (55.0 mL, 54.699 mmol, 3.00 equiv, 1N) in methanol (100 mL) and water (100 mL) under nitrogen was placed in an ice bath and vigorously stirred (1000 rpm) for 1 h, after which pre-chilled commercial aqueous bleach (46.0 mL, 31.909 mmol, 1.75 equiv, 5.2% w / w) was added dropwise over 10 min. At this point, the opaque pale yellow mixture was stirred at 0 °C for 2 h, the mixture was removed from the ice-water bath and stirred at 23 °C for 4 h, solid NaH2PO4 (10 g) was added, followed by the addition of saturated aqueous Na2SO3 (100 mL) to reduce residual iodine, water (100 mL), the mixture was stirred vigorously for 10 min, diluted with CHCl2 (50 mL), the biphasic yellow mixture was poured into a separatory funnel, the layers were separated, and the organics were washed with aqueous Na2SO3 (2 × 50 mL). The remaining organics were extracted from the aqueous layer with CHCl (2 × 25 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, and purified by silica gel chromatography: 35% CHCl in hexanes - 100% CHCl in hexanes to give o-iodophenol (1.497 g, 4.630 mmol, 25%) as a white solid and starting phenol (2.544 g, 12.885 mmol, 71%) as a white solid. NMR indicated pure product.

[0350] 1 H NMR (500 MHz, chloroform-d) δ 7.11 (s, 1H), 5.52 (s, 1H).

[0351] Example 114: Polymers obtained from procatalysts The catalytic activity (in terms of quench time and polymer yield) and the resulting polymer properties were evaluated for procatalysts 1 to 50. The polymerization reactions were carried out in a parallel polymerization reactor (PPR).

[0352] Olefin polymerization reactions were initially carried out in parallel polymerization reactors (PPR) using either isolated metal complexes (see the Examples) or in situ generated complexes (ligands (L-1 to L-25) and ZrBn4 or HfBn4 prepared as a 1:1 mixture 30 min prior to the polymerization experiment).

[0353] The catalytic activity (assessed by quench time) and resulting polymer properties were evaluated for procatalysts 1-50 using a parallel pressure reactor (PPR) at 110 °C, first without diethylzinc (DEZ), and then with three different DEZ loadings (0, 1, and 6 μmol) at 110 °C. The activator was 1.5 molar equivalents of [HNMe(C 18 H 37 )2][B(CF5)4], and the scavenger was MMAO-3A in an amount of 500 nmol. The quench time was determined based on the time the reaction reached 50 or 70 psi propylene uptake or after 1800 seconds, whichever came first. The polymerization was then quenched with CO to destroy the catalyst and terminate the experiment. [Table 1-1] [Table 1-2]

[0354] As reported in Table 1, catalytic activity varies for each procatalyst. The change in catalytic activity was attributed to the functional group substitution pattern of the hydroxy anion and / or neutral non-anionic phenyl ether donor or the group ortho to the substituent on the linking bridging unit. In Table 1, activity was evaluated by the quench time in PPR; the shorter or faster the quench time, the more active the catalyst.

[0355] Next, PPR was performed with different DEZ loadings (0, 1, and 6 μmol) for the procatalysts with higher activity, and the catalytic properties of the procatalysts were evaluated by chain transfer using a chain transfer agent (CSA) to produce polypropylene olefin block copolymers (OBC). The procatalysts with higher activity than the other procatalysts were evaluated. The polymer data for these tests are shown in Table 2. [Table 2-1] [Table 2-2] [Table 2-3]

[0356] In the tests reported in Table 2, polypropylene was produced at 110 °C using varying amounts of the chain shuttle transfer agent, diethylene zinc (DEZ or EtZn). DEZ was added in amounts of 1 or 6 μmol. A decrease in molecular weight was observed as the amount of DEZ increased. The decrease in molecular weight as a function of DEZ amount indicates that these catalysts are highly sensitive to chain transfer agents and rapidly undergo chain transfer with these agents. Specifically, Procatalyst, Procatalyst 12, Procatalyst 20, Procatalyst 25, Procatalyst 26, Procatalyst 28, Procatalyst 30, Procatalyst 34, Procatalyst 42, and Procatalyst 44 exhibited the greatest decrease in polymer molecular weight with increasing DEZ. The greatest decrease in polymer molecular weight suggests that these catalysts exhibit the greatest chain transfer rates, as shown in Table 3.

[0357] Chain shuttle activity The chain transfer ability of a catalyst is first evaluated by running trials of varying the level of chain transfer or chain shuttle agent (CSA) to observe the molecular weight reduction and PDI narrowing expected for a shuttle catalyst. The molecular weight of polymers produced by catalysts that are likely to be good chain shuttle agents is more sensitive to the addition of CSA than the molecular weight of polymers produced by poorer shuttle catalysts. The Mayo equation (Equation 1) shows that a chain transfer agent increases the natural number average chain length in the absence of a chain transfer agent. [ka] to number average chain length [ka] Equation 2 defines the chain transfer or chain shuttle constant, Ca, as the ratio of the chain transfer constant and the propagation rate constant. Equation 3 defines the expected M in a polymerization: n Indicates M no is the original molecular weight of the catalyst in the absence of a chain shuttling agent, and M n is the observed molecular weight of the chain shuttling agent (M n = M without chain shuttle agent no ).

number

[0358] Narrow or minimal changes in PDI confirm that the procatalysts may undergo reversible chain transfer due to CSA. In contrast, broad PDIs indicate irreversible chain transfer. As the amount of DEZ increased, a decrease in PDI or a persistently relatively narrow PDI was observed for most of these procatalysts. In these preliminary PPR experiments, the procatalysts, namely, Procatalyst 6, Procatalyst 22, Procatalyst 23, Procatalyst 24, Procatalyst 32, and Procatalyst 48, showed a significant increase in PDI with increasing DEZ content, indicating irreversible chain transfer due to DEZ.

[0359] The procatalyst is capable of producing polypropylene-based polymers with a range of molecular weights and stereoregularities as measured by TM. The present invention includes the following aspects. Section 1. 1. A polymerization process comprising: In a reactor containing a catalyst system, propylene and / or one or more (C4-C 12 ) contacting an α-olefin, wherein the catalyst system comprises a metal-ligand complex according to formula (I): [ka] During the ceremony, M is a metal selected from titanium, zirconium, or hafnium, said metal having a formal oxidation state of +2, +3, or +4; Each X is independently an unsaturated (C2-C 20 ) Hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (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 is a monodentate or bidentate ligand selected from n is 1 or 2, Each Y is -O-, -S- or -N(R N )- and Each R 1 are independently -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )NC(O)—, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV); [ka] In the formula, R 31~35 , R 41~48 , and R 51~59 Each of the following is independently 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C)2NC(O)—, halogen or —H; However, at least one R in formula (I) 1 is a radical having formula (II), a radical having formula (III), or a radical having formula (IV), 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-) in which R Q However, (C1-C 20 ) hydrocarbyl, Each z1 and z2 is independently sulfur, oxygen, -N(R Z )- and -C(R Z )-, R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b and R 7b are independent, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C6-C 50 ) aryl, (C4-C 50 ) heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, -P(O)(R P )2, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (RC )2NC(O)-, halogen and -H, optionally R 4a and R 5a , or R 5a and R 6a , or R 6a and R 7a , or R 4b and R 5b , or R 5b and R 6b , or R 6b and R 7b may be covalently linked to form an aromatic or non-aromatic ring; Each R in formula (I) C , R N , R Z and R P are independent, (C1-C 20 ) hydrocarbyl, (C1-C 20 ) a polymerization process in which the heterohydrocarbyl is selected from the group consisting of -H. Section 2. Each z1 is sulfur and each z2 is -C(R Z )- and R Z Item 1. The polymerization process of item 1, wherein is (C1-C8) alkyl or -H. Section 3. Each z2 is sulfur and each z1 is -C(R Z )- and R Z Item 1. The polymerization process of item 1, wherein is (C1-C8) alkyl or -H. Section 4. Item 10. The polymerization process of any one of the preceding items, wherein each Y is oxygen. Section 5. Item 11. The polymerization process of any one of the preceding items, wherein the catalyst system further comprises one or more co-catalysts. Section 6. Each R 1 is a radical having formula (III), wherein R 41~48 At least one of (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -OR C , -SR C, —NO 2 , —CN, —CF 3 or a halogen. Section 7. Each R 1 is a radical having formula (III) (1)R 42 and R 47 are independent, (C1-C 20 ) alkyl, -Si(R C )3, -CF3 or halogen, and R 43 and R 46 is -H, or (2)R 43 and R 46 are independent, (C1-C 20 ) alkyl, (C6-C 40 ) aryl, (C5-C 40 ) heteroaryl, -Si(R C )3, -CF3 or halogen, and R 42 and R 47 Item 7. The polymerization process according to any one of items 1 to 6, wherein is —H. Section 8. Each R 1 is a radical having formula (IV), wherein R 51~59 At least one of (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -OR C , -SR C Item 6. The polymerization process according to any one of items 1 to 5, wherein the alkyl group is selected from the group consisting of —NO 2 , —CN, —CF 3 , and halogen. Section 9. Each R 1 is a radical having formula (IV), wherein R 53 , R 55 and R 57 At least one of (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -OR C , -SR CItem 6. The polymerization process according to any one of items 1 to 5, wherein the alkyl group is —NO 2 , —CN, —CF 3 or a halogen. Section 10. Each R 1 Item 6. The polymerization process according to any one of items 1 to 5, wherein is a radical having formula (II): Section 11. Each R 1 is a radical having formula (II), wherein R 32 and R 34 are independent, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -OR C , -SR C Item 6. The polymerization process according to any one of items 1 to 5, wherein the alkyl group is —NO 2 , —CN, —CF 3 or a halogen. Section 12. Each R 1 is a radical having formula (II), wherein R 32 and R 34 are independent, (C1-C 20 ) alkyl, substituted (C6-C 20 ) aryl or unsubstituted (C6-C 20 Item 6. The polymerization process according to any one of items 1 to 5, wherein the aryl is aryl. Section 13. Each R 1 is a radical having formula (II), wherein R 32 and R 34 Item 6. The polymerization process according to any one of items 1 to 5, wherein each is independently tert-butyl, phenyl, 3,5-di(tert-butyl)phenyl, 2,4,6-trimethylphenyl, or 2,4,6-tri(isopropyl)phenyl. Section 14. When Q is (C-C) alkylene, R 4a , R 5a , R 6a , R 7a , R 4b , R 5b , R 6b and R 7b At least two of the50 ) aryl, (C4-C 50 ) heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, -P(O)(R P )2, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C 2. The polymerization process of any one of the preceding claims, wherein the alkyl group is selected from the group consisting of NC(O)— and halogen. Section 15. Q is (-CH2Si(R Q )2CH2-), (-CH2CH2Si(R Q )2CH2CH2-), (-CH2Ge(R Q )2CH2-) or (-CH2CH2Ge(R Q )2CH2CH2-) in which R Q Item 14. The polymerization process according to any one of items 1 to 13, wherein is (C1-C5) alkyl. Section 16. Item 11. The polymerization process of any one of the preceding items, wherein the reactor has a reactor temperature of 140°C or greater. Section 17. Item 11. The polymerization process of any one of the preceding items, wherein the polymer process further comprises solution polymerization, and wherein the solution polymerization is conducted at a pressure of from 10 psi to 2000 psi. Section 18. 18. The polymerization process of any one of paragraphs 1 to 17, wherein the reactor further comprises a chain transfer or chain shuttle agent therein in combination with the catalyst system. Section 19. 21. The polymerization process of claim 20, wherein the chain transfer or chain shuttle agent is diethyl zinc.

Claims

1. 1. A polymerization process comprising: In a reactor containing a catalyst system, propylene and any one or more (C ４ -C １２ ) contacting an α-olefin with a catalyst system comprising a chain transfer or chain shuttle agent, a metal-ligand complex according to formula (I) below, and one or more cocatalysts: 【Chemistry 1】 During the ceremony, M is a metal selected from titanium, zirconium, or hafnium, said metal having a formal oxidation state of +2, +3, or +4; Each X is independently an unsaturated (C ２ -C ２０ ) Hydrocarbon, unsaturated (C ２ -C ５０ ) heterohydrocarbons, (C １ -C ５０ ) hydrocarbyl, (C ６ -C ５０ ) aryl, (C ６ -C ５０ ) heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C ４ -C １２ ) Diene, halogen, -OR Ｃ , -N(R Ｎ ) ２ and -NCOR Ｃ is a monodentate or bidentate ligand selected from n is 1 or 2; each Y is -O- or -S-; Each R １ are independently selected from the group consisting of a radical having formula (II), a radical having formula (III), and a radical having formula (IV); 【Chemistry 2】 In the formula, R ３１～３５ , R ４１～４８ , and R ５１～５９ Each of the groups independently represents １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -N=CHR Ｃ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ ) -, (R Ｃ ) ２ is selected from NC(O)—, halogen or —H; Q is (C １ -C １２ ) alkylene, (C １ -C １２ ) heteroalkylene, (-CH ２ Si(R Ｑ ) ２ CH ２ -), (-CH ２ CH ２ Si(R Ｑ ) ２ CH ２ CH ２ -), (-CH ２ Ge(R Ｑ ) ２ CH ２ -), or (-CH ２ CH ２ Ge(R Ｑ ) ２ CH ２ CH ２ -), wherein R Ｑ However, (C １ -C ２０ ) hydrocarbyl, Each Z １ and Z ２ are independently sulfur, oxygen, -N(R Ｚ )- and -C(R Ｚ )-, provided that the group Z １ and Z ２ In each individual ring containing Z １ and Z ２ is sulfur; R ４ａ , R ５ａ , R ６ａ , R ７ａ , R ４ｂ , R ５ｂ , R ６ｂ , and R ７ｂ is independent, (C １ -C ５０ ) hydrocarbyl, (C １ -C ５０ ) heterohydrocarbyl, (C ６ -C ５０ ) aryl, (C ４ -C ５０ ) heteroaryl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, -P(O)(R Ｐ ) ２ , R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ ) -, (R Ｃ ) ２ is selected from NC(O)—, halogen and —H, and optionally R ４ａ and R ５ａ , or R ５ａ and R ６ａ , or R ６ａ and R ７ａ , or R ４ｂ and R ５ｂ , or R ５ｂ and R ６ｂ , or R ６ｂ and R ７ｂ may be covalently linked to form an aromatic or non-aromatic ring; Each R in formula (I) Ｃ , R Ｎ , R Ｚ and R Ｐ is independent, (C １ -C ２０ ) hydrocarbyl, (C １ -C ２０ ) selected from the group consisting of heterohydrocarbyl and -H; A polymerization process wherein the chain transfer or shuttle agent comprises a first metal which is Al, B or Ga, the first metal being in a formal oxidation state of +3, or a second metal which is Zn or Mg, the second metal being in a formal oxidation state of +2.

2. Each Z １ is sulfur, and each Z ２ -C(R Ｚ )-, and R Ｚ But (C １ -C ８ 2. The polymerization process of claim 1 , wherein:

3. Each Z ２ is sulfur, and each Z １ -C(R Ｚ )-, and R Ｚ But (C １ -C ８ 2. The polymerization process of claim 1 , wherein:

4. The polymerization process of any one of claims 1 to 3, wherein each Y is oxygen.

5. Each R １ is a radical having the formula (III), ４１～４８ At least one of (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ or a halogen.

6. Each R １ is a radical having the formula (III) (1) R ４２ and R ４７ is independent, (C １ -C ２０ ) alkyl, —Si(R Ｃ ) ３ , -CF ３ or halogen; R ４３ and R ４６ is -H, or (2) R ４３ and R ４６ is independent, (C １ -C ２０ ) alkyl, (C ６ -C ４０ ) aryl, (C ５ -C ４０ ) heteroaryl, —Si(R Ｃ ) ３ , -CF ３ or halogen; R ４２ and R ４７ The polymerization process of any one of claims 1 to 5, wherein is -H.

7. Each R １ is a radical having the formula (IV), where R ５１～５９ At least one of (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ or a halogen.

8. Each R １ is a radical having the formula (IV), where R ５３ , R ５５ and R ５７ At least one of (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ or a halogen.

9. Each R １ The polymerization process according to any one of claims 1 to 4, wherein is a radical having the formula (II).

10. Each R １ is a radical having the formula (II), ３２ and R ３４ is independent, (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ or a halogen.

11. Each R １ is a radical having the formula (II), ３２ and R ３４ is independent, (C １ -C ２０ ) alkyl, substituted (C ６ -C ２０ ) aryl or unsubstituted (C ６ -C ２０ 5. The polymerization process of claim 1, wherein the aryl is aryl.

12. Each R １ is a radical having the formula (II), where R ３２ and R ３４ The polymerization process of any one of claims 1 to 4, wherein is independently tert-butyl, phenyl, 3,5-di(tert-butyl)phenyl, 2,4,6-trimethylphenyl, or 2,4,6-tri(isopropyl)phenyl.

13. Q is (C ３ -C ４ ) alkylene, R ４ａ , R ５ａ , R ６ａ , R ７ａ , R ４ｂ , R ５ｂ , R ６ｂ and R ７ｂ At least two of (C ６ -C ５０ ) aryl, (C ４ -C ５０ ) heteroaryl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, -P(O)(R Ｐ ) ２ , R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ ) -, (R Ｃ ) ２ The polymerization process of any one of claims 1 to 12, wherein the alkyl group is selected from the group consisting of NC(O)- and halogen.

14. Q is (-CH ２ Si(R Ｑ ) ２ CH ２ -), (-CH ２ CH ２ Si(R Ｑ ) ２ CH ２ CH ２ -), (-CH ２ Ge(R Ｑ ) ２ CH ２ -) or (-CH ２ CH ２ Ge(R Ｑ ) ２ CH ２ CH ２ -), wherein R Ｑ But (C １ -C ５ 14. The polymerization process of claim 1, wherein:

15. The polymerization process according to any one of claims 1 to 14, wherein the reactor has a reactor temperature of 140°C or higher.

16. 16. The polymerization process of any one of claims 1 to 15, further comprising a solution polymerization, wherein the solution polymerization is carried out at a pressure of from 10 psi to 2000 psi.

17. The polymerization process according to any one of claims 1 to 16, wherein the chain transfer or shuttle agent is diethyl zinc.

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