Modified pyridine-2,6-bis(phenylenephenolate) complexes with enhanced solubility useful as catalyst components for olefin polymerization

Abstract

Exemplary embodiments of the industrial advances of the present invention include pyridine-2,6-bis(phenylenephenolate) complexes that are useful as catalyst components for olefin polymerization and have increased solubility in non-aromatic hydrocarbons (e.g., isohexane). The improved solubility of these complexes was achieved through modification of the leaving group, which generally results in improved solubility without adversely affecting the performance of the complexes when used as catalysts for olefin polymerization.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 338,173, filed May 4, 2022, the disclosure of which is incorporated herein by reference. The present disclosure relates to bis(arylphenolate) Lewis base transition metal complexes, catalyst systems including bis(arylphenolate) Lewis base transition metal complexes, and polymerization methods for producing polyolefin polymers, such as polyethylene- and polypropylene-based polymers. [Background technology]

[0002] Polyolefins such as polyethylene typically have a comonomer, such as hexene, incorporated into the polyethylene backbone. These copolymers provide different physical properties compared to polyethylene alone and are typically produced in low pressure reactors using, for example, solution, slurry or gas phase polymerization processes. The polymerization can be carried out in the presence of a catalyst system, such as a catalyst system using a Ziegler-Natta catalyst, a chromium-based catalyst or a metallocene catalyst. Furthermore, since the precatalyst (neutral unactivated complex) is often stored for several weeks before use, the precatalyst should be thermally stable at ambient temperature or above. The performance of a given catalyst is closely affected by reaction conditions such as monomer concentration and temperature. For example, solution processes that benefit from operating at temperatures above 120° C. are particularly challenging for catalyst development. At such high reactor temperatures, it is often difficult to maintain high catalyst activity and high molecular weight capability, as both attributes decrease very consistently with increasing reactor temperature. For a wide range of desired polyolefin products, ranging from high density polyethylene (HDPE) to elastomers (e.g., thermoplastic elastomers (TPE); ethylene-propylene-diene (EPDM)), a large number of different catalyst systems may be required, since a single catalyst is unlikely to be able to address all the needs for the production of these various polyolefin products. The stringent set of requirements necessary for the development and production of new polyolefin products makes the effort to identify a suitable catalyst for a given product and production process very challenging.

[0003] Aromatic solvents are typically used to dissolve catalyst components in industrial olefin polymerization processes, but replacing aromatic solvents with non-aromatic solvents such as isohexane is challenging because the catalyst components usually have poor solubility in non-aromatic solvents. Further information regarding the general state of the art regarding nonmetallocene olefin polymerization catalysts can be found in Baier, MC (2014) "Post-Metallocenes in the Industrial Production of Poly-olefins," Angew. Chem. Int. Ed., v.53, pp. 9722-9744, the entire contents of which are incorporated herein by reference.

[0004] Further information regarding the complexes can be found in Goryunov, GP et al. (2021) "Rigid Postmetallocene Catalysts for Propylene Polymerization: Ligand Design Prevents the Temperature-Dependent Loss of Stereo- and Regioselectivities," ACS Catalysis, v.11(13), pp. 8079-8086; US2020 / 0255556; US2020 / 0255555; US2020 / 0254431; and US2020 / 0255553, each of which is incorporated by reference in its entirety. Summary of the Invention

[0005] A catalyst compound represented by formula (I): [ka] (I) (In the formula, M is a Group 3, 4 or 5 metal; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 Or R 7 and R 8may be joined together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, heteroatom or heteroatom-containing group, or adjacent R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 any two or more of may be taken together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 are each independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 Or R 17 and R 19 may be joined together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; L is a Lewis base, each X is independently a hydrocarbyl or substituted hydrocarbyl ligand, and at least one X is a non-aromatic hydrocarbyl ligand having 9 or more carbon atoms, or a substituted hydrocarbyl ligand having at least 5 or more carbon atoms, or when n is 2, both X's together may be hydrocarbyl or substituted hydrocarbyls containing 4 or more carbon atoms and forming a 5-membered cyclic ring structure with M; n is 1, 2 or 3; m is 0, 1 or 2; n+m is equal to or less than 4, any two L groups may be linked together to form a bidentate Lewis base; The X group may be linked to the L group to form a monoanionic bidentate group.

[0006] an aliphatic hydrocarbon solvent; and at least one complex of formula (I), wherein the concentration of the complex is 0.20% by weight or more (alternatively 0.25% by weight or more, alternatively 0.30% by weight or more, alternatively 0.35% by weight or more, alternatively 0.40% by weight or more, alternatively 0.50% by weight or more, alternatively 1.0% by weight or more, alternatively 2.0% by weight or more). A method for producing a propylene-based polymer comprising the step of polymerizing propylene in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. by contacting the propylene with a catalyst system made from formula (I) to form a propylene-based polymer. A process for producing an ethylene-based polymer comprising the step of polymerizing ethylene in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa, and a reactor temperature of 30° C. to 230° C. by contacting the ethylene with a catalyst system made from formula (I) to form a propylene-based polymer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] Exemplary embodiments of the industrial advances of the present invention include pyridine-2,6-bis(phenylenephenolate) complexes that are useful as catalyst components for olefin polymerization and have increased solubility in non-aromatic hydrocarbons (e.g., isohexane). The improved solubility of these complexes was achieved through modification of the leaving group, which generally results in improved solubility without adversely affecting the performance of the complexes when used as catalysts for olefin polymerization. For purposes of this disclosure, the numbering scheme for the Periodic Table Groups will be used as set forth in Chemical and Engineering News, v.63(5), pg. 27 (1985). Thus, a "Group 4 metal" refers to an element in Group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.

[0008] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Ph is phenyl, tBu is tertiary butyl, and Tf is triflate (-SO 2 CF 3 ), Ad is adamantanyl, MAO is methylalumoxane, NMR is nuclear magnetic resonance, t is time, s is seconds, h is hours, psi is pounds per square inch, psig is pounds per square inch gauge, equiv is equivalent, and RPM is revolutions per minute.

[0009] This specification describes transition metal complexes. The term complex is used to describe molecules in which ancillary ligands are coordinated to a central transition metal atom. The ligands are bulky and stably bound to the transition metal so as to maintain their influence during the use of the catalyst, such as polymerization. The ligands can be coordinated to the transition metal by covalent and / or electron donating coordination or intermediate bonds. Transition metal complexes are generally activated to perform their polymerization or oligomerization functions using an activator, which, without being bound by theory, is believed to generate a cation as a result of removal of an anionic group, often referred to as a leaving group, from the transition metal. The terms "substituents," "radicals," "groups," and "moieties" may be used interchangeably. "Conversion" refers to the amount of monomer that is converted to polymer product, reported as mol %, and calculated based on the polymer yield and the amount of monomer fed to the reactor.

[0010] "Catalytic activity" is a measure of how active a catalyst is and is expressed as grams of product polymer (P) produced per millimole of catalyst (cat) per hour (gP.mmolcat -1 .h -1 ) The term "heteroatom" refers to any of the elements in Groups 13-17, except carbon. Heteroatoms can include B, Si, Ge, Sn, N, P, As, O, S, Se, Te, F, Cl, Br, and I. The term "heteroatom" refers to any of the above elements having a hydrogen bonded thereto, such as BH, BH 2 , SiH 2 , OH, NH, NH 2 The term "substituted heteroatom" describes a heteroatom having one or more of its hydrogen atoms replaced by a hydrocarbyl group or a substituted hydrocarbyl group.

[0011] Unless otherwise indicated (e.g., in the definitions of "substituted hydrocarbyl," "substituted aromatic," etc.), the term "substituted" means that at least one hydrogen atom has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group, such as -NR * 2 , -OR * , -SeR * , -TeR * , -PR * 2 , -AsR * 2 , -SbR * 2 , -SR * , -BR * 2 , -SiR * 3 , -GeR * 3 , -SnR * 3 , -PbR * 3 and R * are each independently a hydrocarbyl radical or a halocarbyl radical, and two or more R * means that the hydrocarbyl ring is replaced by at least one non-hydrogen group such as aryl, aryloxy ...

[0012] The term "substituted hydrocarbyl" refers to a hydrocarbyl radical in which at least one hydrogen atom has been replaced with at least one heteroatom (e.g., a halogen, such as Br, Cl, F, or I) or heteroatom-containing group (e.g., a functional group, such as -NR * 2 , -OR * , -SeR * , -TeR * , -PR * 2 , -AsR * 2 , -SbR *2 , -SR * , -BR * 2 , -SiR * 3 , -GeR * 3 , -SnR * 3 , -PbR * 3 and R * are each independently a hydrocarbyl radical or a halocarbyl radical, and two or more R * means a hydrocarbyl radical replaced by a heteroatom which may be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or a hydrocarbyl radical in which at least one heteroatom is inserted within the hydrocarbyl ring. The term "hydrocarbyl-substituted phenyl" means a phenyl group in which one, two, three, four or five hydrogen radicals have been replaced by a hydrocarbyl or substituted hydrocarbyl group. For example, a "hydrocarbyl-substituted phenyl" group can be represented by the formula:

[0013] [ka] (R a , R b , R c , R d and R e are hydrogen, C 1 -C 40 Hydrocarbyl or C 1 -C 40 Substituted hydrocarbyl, heteroatom or heteroatom-containing group (wherein R a , R b , R c , R d and R e at least one of R a , R b , R c , R d and R e Two or more of these together form C 4 -C62 may form cyclic or polycyclic hydrocarbyl ring structures or combinations thereof It can be expressed as: The term "substituted aromatic" means an aromatic group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0014] The term "substituted phenyl" means a phenyl group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. The term "substituted carbazole" refers to a carbazolyl group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. The term "substituted naphthyl" means a naphthyl group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. The term "substituted anthracenyl" refers to an anthracenyl group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. The term "substituted fluorenyl" refers to a fluorenyl group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0015] The terms trihydrocarbylsilyl and trihydrocarbylgermyl refer to a silyl or germyl group bonded to three hydrocarbyl groups. Examples of suitable trihydrocarbylsilyl and trihydrocarbylgermyl groups include trimethylsilyl, trimethylgermyl, triethylsilyl, triethylgermyl, and all isomers of tripropylsilyl, tripropylgermyl, tributylsilyl, tributylgermyl, tripentylsilyl, tripentylgermyl, butyldimethylsilyl, butyldimethylgermyl, dimethyloctylsilyl, dimethyloctylgermyl, and the like. The terms dihydrocarbylamino and dihydrocarbylphosphino refer to a nitrogen or phosphorus group bonded to two hydrocarbyl groups. Examples of suitable dihydrocarbylamino and dihydrocarbylphosphino groups may include dimethylamino, dimethylphosphino, diethylamino, diethylphosphino, and all isomers of dipropylamino, dipropylphosphino, dibutylamino, dibutylphosphino, and the like.

[0016] The term "substituted adamantanyl" refers to an adamantanyl group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. The terms "alkoxy" and "alkoxide" refer to an alkyl or aryl group bonded to an oxygen atom, e.g., an alkyl ether or aryl ether group / radical bonded to an oxygen atom, wherein the alkyl / aryl group is selected from the group consisting of C 1 ~C 10 The alkyl groups may include those that are hydrocarbyl (also referred to as hydrocarbyloxy groups). The alkyl groups may be linear, branched or cyclic. The alkyl groups may be saturated or unsaturated. Examples of suitable alkoxy radicals may include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, phenoxy. The term "aryl" or "aryl group" refers to aromatic rings and substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Similarly, heteroaryl refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) is replaced by a heteroatom such as N, O or S. As used herein, the term "aromatic" also refers to pseudoheteroaromatic rings, which are heterocyclic substituents with similar properties and structure (nearly planar) to aromatic heterocyclic ligands, but which are not according to the definition of aromatic. Similarly, the term aromatic also refers to substituted aromatics.

[0017] The term "arylalkyl" refers to an aryl group in which a hydrogen is replaced by an alkyl group or a substituted alkyl group. For example, 3,5'-di-tert-butyl-phenylindenyl is an indene substituted by an arylalkyl group. When an arylalkyl group is a substituent on another group, the arylalkyl group is bonded to the other group through the aryl. The term "alkylaryl" refers to an alkyl group in which a hydrogen has been replaced by an aryl group or a substituted aryl group. For example, phenethylindenyl is an indene substituted with an ethyl group attached to a benzene group. When an alkylaryl group is a substituent on another group, the alkylaryl group is attached to the other group via the alkyl. The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has 6 ring atoms and a tetrahydrofuran has 5 ring atoms.

[0018] A heterocycle is a ring that has a heteroatom in the ring structure, as opposed to a heteroatom-substituted ring, in which a hydrogen atom on a ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocycle, and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles can include pyridine, imidazole, and thiazole.

[0019] The terms "hydrocarbyl radical", "hydrocarbyl group" or "hydrocarbyl" may be used interchangeably and are defined to mean a group consisting solely of hydrogen and carbon atoms. For example, a hydrocarbyl may be linear, branched or cyclic, and if cyclic, may be aromatic or non-aromatic. 1 -C 100Examples of such radicals include, but are not limited to, alkyl groups such as methyl, ethyl, propyl (e.g., n-propyl, isopropyl, cyclopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., iso-amyl, cyclopentyl), hexyl (e.g., cyclohexyl), octyl (e.g., cyclooctyl), nonyl, decyl (e.g., adamantanyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, or tricontyl, and aryl groups such as phenyl, benzyl, and naphthyl. As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol.

[0020] Unless otherwise indicated, as used herein, "high molecular weight" is defined as a number average molecular weight (Mn) value of 100,000 g / mol or greater. "Low molecular weight" is defined as a Mn value of less than 100,000 g / mol. Unless otherwise stated, all melting points (Tm) are second run melting points of differential scanning calorimetry (DSC).

[0021] A "catalyst system" is a combination of at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material. The terms "catalyst compound", "catalyst complex", "transition metal complex", "transition metal compound", "pre-catalyst compound" and "pre-catalyst complex" are used interchangeably. When "catalyst system" is used to describe such a pair prior to activation, "catalyst system" refers to the unactivated catalyst complex (pre-catalyst) together with an activator, and optionally together with a co-activator. When "catalyst system" is used to describe such a pair after activation, "catalyst system" refers to the activated complex and the activator or other charge-balancing moiety. The transition metal compound may be neutral, as in a pre-catalyst, or may be a charged species with a counterion, as in an activated catalyst system. For purposes of this disclosure and claims thereto, when a catalyst system is described as including neutral stable forms of the components, it is well understood by those skilled in the art that the ionic forms of the components are the forms that react with monomers to produce polymers. A polymerization catalyst system is a catalyst system capable of polymerizing monomers into polymers. Additionally, the catalyst compounds and activators represented by formulas herein are intended to encompass both the neutral and ionic forms of the catalyst compounds and activators.

[0022] In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a pre-catalyst compound, a catalyst compound, or a transition metal compound, and these terms are used interchangeably. An "anionic ligand" is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A "Lewis base" is a neutrally charged ligand that donates one or more pairs of electrons to a metal ion. Examples of Lewis bases include diethyl ether, trimethylamine, pyridine, tetrahydrofuran, dimethylsulfide, and triphenylphosphine. The term "heterocyclic Lewis base" refers to a Lewis base that is also a heterocycle. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan. Bis(arylphenolate) Lewis base ligands are tridentate ligands that bind to metals via two anionic donors (phenolates) and one heterocyclic Lewis base donor (e.g., a pyridinyl group). Bis(arylphenolate) heterocyclic ligands are tridentate ligands that bind to metals via two anionic donors (phenolates) and one heterocyclic Lewis base donor. The term "continuously" refers to a system that operates without interruption or cessation. For example, a continuous process for producing a polymer is one in which reactants are continuously introduced into one or more reactors and polymer product is continuously removed.

[0023] Transition metal complexes In at least one embodiment, the catalyst compound represented by formula (I) is as follows: [ka] (I) (In the formula, M is a Group 3, 4 or 5 metal; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 Or R 7 and R 8 may be joined together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, heteroatom or heteroatom-containing group, or adjacent R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 any two or more of may be taken together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 are each independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 17 and R18 , R 18 and R 19 Or R 17 and R 19 may be joined together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; L is a Lewis base, each X is independently a hydrocarbyl or substituted hydrocarbyl ligand, and at least one X is a non-aromatic hydrocarbyl ligand having 9 or more carbon atoms, or a substituted hydrocarbyl ligand having at least 5 or more carbon atoms, or when n is 2, both X's together may be hydrocarbyl or substituted hydrocarbyls containing 4 or more carbon atoms and forming a 5-membered cyclic ring structure with M; n is 1, 2 or 3; m is 0, 1 or 2; n+m is equal to or less than 4, any two L groups may be linked together to form a bidentate Lewis base; The X group may be linked to the L group to form a monoanionic bidentate group).

[0024] When n is 2, both X's taken together can be represented by the following formula Ia, Ib, Ic or Id, wherein R 20 , R 20’ , R 21 , R 21’ , R 22 , R 22’ , R 23 , R 23’ are independently hydrogen or C 1 -C 20 is a hydrocarbyl, and the dashed line represents the bond to the metal atom M. [ka]

[0025] For example, M in formula (I) can be a metal of Group 3, Group 4, or Group 5, e.g., M can be a Group 4 metal. Group 4 metals can include zirconium, titanium, and hafnium. In at least one embodiment, M is zirconium or hafnium.

[0026] In formula (I), L is an ether, an amine, a phosphine, a thioether, an ester (e.g., Et 2 O, MeOtBu, etc.), Et 3 N, PhNMe 2 , MePh 2 They can be independently selected from N, tetrahydrofuran, methyl acetate and dimethyl sulfide.

[0027] R in formula (I) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen and C 1 -C 40 Hydrocarbyl, C 1 -C 40 or R may be independently selected from substituted hydrocarbyl, hydrocarbyloxy, trihydrocarbylsilyl, trihydrocarbylgermyl, dihydrocarbylamino, dihydrocarbylphosphino, or halogen; 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 Or R 7 and R 8 may be joined to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms.

[0028] In at least one embodiment, R of formula (I) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 one or more of the following may be selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, substituted phenyl, biphenyl or their isomers, which may be halogenated (e.g., perfluoropropyl, perfluorobutyl, perfluoroethyl, perfluoromethyl), substituted hydrocarbyl radicals, and all isomers of substituted hydrocarbyl radicals, including trimethylsilylpropyl, trimethylsilylmethyl, trimethylsilylethyl, phenyl, or all isomers of hydrocarbyl substituted phenyl, including methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, heteroatom-containing groups (including trimethylsilyl, triethylsilyl, methoxy, ethoxy, cyclohexyloxy, trifluoromethyl, dimethylamino, diethylamino, dicyclohexylamino), and all isomers of tripropylsilyl, tributylsilyl, tripentylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, dimethyloctylsilyl, butyldimethylsilyl (e.g., t-butyldimethylsilyl), propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, and the like.

[0029] For example, R in formula (I) 4 and R 5 is independently 1 -C 20 It can be alkyl, e.g., R 4 and R 5can be tert-butyl or adamantanyl. In at least one embodiment, R 4 and R 5 are independently selected from unsubstituted phenyl, substituted phenyl, unsubstituted carbazole, substituted carbazole, unsubstituted naphthyl, substituted naphthyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted fluorenyl or substituted fluorenyl, a heteroatom or a heteroatom-containing group, e.g., R 4 and R 5 can be independently unsubstituted phenyl or 3,5-di-tert-butylbenzyl. 4 is C 1 -C 20 can be alkyl (e.g., R 4 can be tert-butyl), R 5 can be aryl, or (2) R 5 is C 1 -C 20 can be alkyl (e.g., R 5 can be tert-butyl) and R 4 Alternatively, R can be aryl. 4 and / or R 5 can independently be a heteroatom, for example, R 4 and R 5 can be a halogen atom (e.g., Br, Cl, F or I). Alternatively, R 4 and / or R 5 can independently be a silyl group, e.g., R 4 and R 5 can be a trialkylsilyl group or a triarylsilyl group, where alkyl is C 1 ~C 30alkyl (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl, cyclopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., iso-amyl, cyclopentyl), hexyl (e.g., cyclohexyl), octyl (e.g., cyclooctyl), nonyl, decyl (e.g., adamantanyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, or tricontyl); aryl is C 6 ~C 30 aryl (e.g., phenyl, benzyl and naphthyl). Usefully, R 4 and R 5 can be triethylsilyl.

[0030] In some embodiments, R 4 and R 5 is independently 1 -C 40 Hydrocarbyl, C 1 -C 40 More preferably, R 4 and R 5 are each independently selected from tertiary hydrocarbyl groups (e.g., tert-butyl, tert-pentyl, tert-hexyl, tert-heptyl, tert-octyl, tert-nonyl, tert-decyl, tert-undecyl, tert-dodecyl) and cyclic tertiary hydrocarbyl groups (e.g., 1-methylcyclohexyl, 1-norbornyl, 1-adamantanyl, or substituted 1-adamantanyl).

[0031] In some embodiments, R 4 and R 5 is independently 1 -C 40 Hydrocarbyl, C 1 -C 40 More preferably, R4 and R 5 is each independently a non-aromatic cyclic alkyl group (e.g., cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, adamantanyl, norbornyl, or 1-methylcyclohexyl or substituted adamantanyl), most preferably a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, 1-adamantanyl, substituted 1-adamantanyl, or 1-norbornyl).

[0032] In some embodiments, R 4 and R 5 C includes, independently, trimethylsilyl, triethylsilyl, and all isomers such as tripropylsilyl, tributylsilyl, tripentylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, dimethyloctylsilyl, and butyldimethylsilyl. 3 -C 30 It is a heteroatom-containing group. R 4 and R 5 The molecular weight of the polymer product can be controlled by using the values ​​of R 4 and R 5 When one or both of R are tert-butyl, the catalyst compound can provide high molecular weight polymers. 4 , R 5 , or R 4 and R 5 When is phenyl, the catalyst compound can give low molecular weight polymers. In at least one embodiment, R of formula (I) 2 and R 7 are each independently 1 -C 10 is alkyl, e.g., R 2 and R 7 are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dimethyl-pentyl, tert-butyl, isopropyl or an isomer thereof.

[0033] In at least one embodiment, R of formula (I) 2 and R 7 are each independently 3 -C 30 Substituted hydrocarbyl or C 3 -C 30 Heteroatom-containing groups, such as R 2 and R 7 are independently trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, trioctylsilyl, dimethyloctylsilyl, butyldimethylsilyl (including t-butyldimethylsilyl), methyltrimethylsilyl, or an isomer thereof. R in formula (I) 1 , R 3 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 Each independently represents hydrogen or C 1 -C 10 It can be alkyl, e.g., R 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 15 , R 16 , R 17 , R 18 and R 19 can be independently hydrogen, methyl, ethyl, propyl, or isopropyl. In at least one embodiment, R 1 , R 3 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R14 , R 15 , R 16 , R 17 , R 18 and R 19 is hydrogen. Alternatively, R in formula (I) 1 , R 3 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 Each may independently be hydrogen, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, or trimethylsilyl.

[0034] Each X can independently be a hydrocarbyl or substituted hydrocarbyl ligand, and at least one of X is 9 -C 40 Non-aromatic hydrocarbyl ligands, alternatively C 9 -C 20 Non-aromatic hydrocarbyl ligands, alternatively C 10 -C 20 Non-aromatic hydrocarbyl ligands, alternatively C 12 -C 20 It is a non-aromatic hydrocarbyl ligand. Each X can independently be a hydrocarbyl or substituted hydrocarbyl ligand, and at least one of X is 9 -C 40 Non-aromatic hydrocarbyl ligands, alternatively C 9 -C 20 Non-aromatic hydrocarbyl ligands, alternatively C 10 -C 20 Non-aromatic hydrocarbyl ligands, alternatively C 12 -C 20 The other X is a non-aromatic hydrocarbyl ligand, 1 -C 40Hydrocarbyl or substituted hydrocarbyl ligands, alternatively C 1 -C 20 It is a hydrocarbyl or substituted hydrocarbyl ligand.

[0035] Each X can independently be a hydrocarbyl or substituted hydrocarbyl ligand, and at least one of X is 9 -C 40 The other X is a non-aromatic hydrocarbyl ligand, 1 -C 40 It is a hydrocarbyl ligand. Each X can independently be a hydrocarbyl ligand, and at least one of X is 9 -C 40 The other X is a non-aromatic hydrocarbyl ligand, 1 -C 40 It is a non-aromatic hydrocarbyl ligand. Each X can independently be a hydrocarbyl ligand, and at least one of X is 9 -C 20 The other X is a non-aromatic hydrocarbyl ligand, 1 -C 20 It is a non-aromatic hydrocarbyl ligand.

[0036] Preferred C for X 9 -C 20Non-aromatic hydrocarbyl ligands include, for example, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosnyl, 2,2-dimethylhept-1-yl, 2,2-dimethyloct-1-yl, 2,2-dimethylnon ... Includes all of the isomers of nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosanyl, such as dimethyldec-1-yl, 3,7-dimethyloct-1-yl, 2-ethyldec-1-yl, 9-methylundec-1-yl, 2-hexyldec-1-yl, 3,7,11-trimethyldodec-1-yl, etc. Preferred C for X 1 -C 20 Non-aromatic hydrocarbyl ligands include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosinyl, 2,2-dimethylhept-1-yl, 2,2-dimethyloct-1-yl, 2,2-dimethylnon-1-yl, 2,2-dimethyl Includes all of the methyl, ethyl, and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosanyl isomers, such as dec-1-yl, 3,7-dimethyloct-1-yl, 2-ethyldec-1-yl, 9-methylundec-1-yl, 2-hexyldec-1-yl, 3,7,11-trimethyldodec-1-yl.

[0037] Each X can independently be a hydrocarbyl ligand, and at least one of X is 10 -C 20 is a non-aromatic hydrocarbyl ligand, and the other X is a non-aromatic C 1 -C20 It is a hydrocarbyl ligand.

[0038] Each X can independently be a hydrocarbyl ligand, and at least one of X is 12 -C 20 is a non-aromatic hydrocarbyl ligand, and the other X is a non-aromatic C 1 -C 20 It is a hydrocarbyl ligand. Each X can independently be a hydrocarbyl or substituted hydrocarbyl ligand, and at least one of X is 5 -C 40 Substituted hydrocarbyl ligands, alternatively C 5 -C 30 Substituted hydrocarbyl ligands, alternatively C 7 -C 30 Substituted hydrocarbyl ligands, alternatively C 10 -C 30 Substituted hydrocarbyl ligands, alternatively C 12 -C 30 It is a substituted hydrocarbyl ligand.

[0039] Each X can independently be a hydrocarbyl or substituted hydrocarbyl ligand, and at least one of X is 5 -C 30 It is a substituted hydrocarbyl ligand. X's preferred C 5 -C 30 The substituted hydrocarbyl ligand is SiR 30 3 , G.E.R. 30 3 , OR 30 , S.R. 30 , N.R. 30 2 R 30are each independently selected from the group consisting of (1,1-dimethylethoxy)oct-8-yl, [(trimethylsilyl)oxy]dec-10-yl, [tert-butyldimethylsilyl)oxy]hex-6-yl, [tert-butyldimethylsilyl)oxy]oct-8-yl, 4-(cyclohexylthio)benzyl, trimethylsilyleth-2-yl, trimethylsilylprop-3-yl, and (triethylsilyl)methyl. 1 -C 10 Alkyl, C 7 -C 10 Alkylaryl or C 7 -C 10 C preferably selected from arylalkyl 1 -C 10 It is a hydrocarbyl.

[0040] X's preferred C 7 -C 30 The substituted hydrocarbyl ligand is SiR 30 3 , G.E.R. 30 3 , OR 30 , S.R. 30 , N.R. 30 2 R 30 are each independently selected from the group consisting of (1,1-dimethylethoxy)oct-8-yl, [(trimethylsilyl)oxy]dec-10-yl, [tert-butyldimethylsilyl)oxy]hex-6-yl, [tert-butyldimethylsilyl)oxy]oct-8-yl, 4-(cyclohexylthio)benzyl, 4-(cyclopentylthio)benzyl, 4-(cycloheptylthio)benzyl, 4-(cyclopentyloxy)benzyl, 4-(cyclohexyloxy)benzyl, 4-(cycloheptyloxy)benzyl, triethylsilyleth-2-yl, trimethylsilylbut-4-yl, and (triethylsilyl)methyl. 1 -C 10 Alkyl, C 7 -C 10 Alkylaryl or C 7 -C10 C preferably selected from arylalkyl 1 -C 10 It is a hydrocarbyl.

[0041] Each X can independently be a hydrocarbyl or substituted hydrocarbyl ligand, and at least one of X is 10 -C 30 It is a substituted hydrocarbyl ligand. X's preferred C 10 -C 30 The substituted hydrocarbyl ligand is SiR 30 3 , G.E.R. 30 3 , OR 30 , S.R. 30 , N.R. 30 2 R 30 are each independently selected from the group consisting of (1,1-dimethylethoxy)oct-8-yl, [(trimethylsilyl)oxy]dec-10-yl, [tert-butyldimethylsilyl)oxy]hex-6-yl, [tert-butyldimethylsilyl)oxy]oct-8-yl, 4-(cyclohexylthio)benzyl, 4-(cyclopentylthio)benzyl, 4-(cycloheptylthio)benzyl, 4-(cyclopentyloxy)benzyl, 4-(cyclohexyloxy)benzyl, 4-(cycloheptyloxy)benzyl, tripropylsilyleth-2-yl, trimethylsilyloct-8-yl, and (tripropylsilyl)methyl. 1 -C 10 Alkyl, C 7 -C 10 Alkylaryl or C 7 -C 10 C preferably selected from arylalkyl 1 -C 10 It is a hydrocarbyl.

[0042] m can be 0, n can be 2, and both X's together form a 5-membered cyclic ring structure with M; 4 -C 40It can be a hydrocarbyl or a substituted hydrocarbyl. m can be 0, n can be 2, and each X can be represented by formula Ic, R 20 , R 20’ , R 21 , R 22 , R 23 , R 23’ are independently hydrogen or C 1 -C 20 It can be a hydrocarbyl. m can be 0, n can be 2, and each X can be represented by formula Ic, R 20 , R 20’ , R 23 , R 23’ can be hydrogen, R 21 and R 22 Each can independently be hydrogen or hydrocarbyl. m can be 0, n can be 2, and each X can be represented by formula Ic, R 20 , R 20’ , R 23 , R 23’ can be hydrogen, R 21 and R 22 One of the groups can be hydrogen and the other can be hydrogen or hydrocarbyl, alternatively hydrogen or C 1 -C 20 Hydrocarbyl, alternatively hydrogen or C 1 -C 10 It is a hydrocarbyl.

[0043] R 21 or R 22Preferred hydrocarbyls for are, for example, methyl, ethyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 3-methylbut-2-yl, cyclopentyl, n-hexyl, isohexyl, 1-methylpent-1-yl, cyclohexyl, n-heptyl, 4-methylpent-3-en-1-yl, 1-methylhex-1-yl, n-octyl, 1-methylhept-1-yl, n-nonyl, n-decyl, n-undecyl, n- Including all of the methyl, ethyl, and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosanyl isomers, such as dodecyl, 4,8-dimethylnona-3,7-dien-1-yl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosanyl.

[0044] m can be 0, n can be 2, and each X can be represented by formula Ic, R 20 , R 20’ , R 23 , R 23’ can be hydrogen, R 21 and R 22 One of the groups can be hydrogen and the other can be C 1 -C 10 It is a hydrocarbyl. m can be 0, n can be 2, and each X can be represented by formula Ic, R 20 , R 20’ , R 23 , R 23’ can be hydrogen, R 21 and R 22 One of the radicals can be hydrogen and the other is selected from hydrogen, methyl, ethyl, and all isomeric forms of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. m can be 0, n can be 2, and each X can be represented by formula Ic, R 20 , R 20’ , R 23 , R 23’ can be hydrogen, R 21 and R 22 One of the groups can be hydrogen and the other is selected from hydrogen, methyl or 4-methylpent-3-en-1-yl. In formula (I), R 4 and R 5 can be adamantanyl, R 2 and R 7 is C 4 -C 40 Hydrocarbyl or C 6 -C 30 can be a heteroatom-containing group, m can be 0, n can be 2, and any of X can be represented by formula Ic.

[0045] In formula (I), R 4 and R 5 can be adamantanyl, R 2 and R 7 is C 4 -C 8 Hydrocarbyl or C 6 -C 20 can be a heteroatom-containing group, m can be 0, n can be 2, and any of X can be represented by formula Ic.

[0046] In formula (I), R 4 and R 5 can be adamantanyl, R 2 and R 7 can be tert-butyl, 1,1-dimethylpropyl, n-octyl, or tert-butyldimethylsilyl, m can be 0, n can be 2, and any of X can be represented by formula Ic. In formula (I), R 4 and R 5 can be adamantanyl, R2 and R 7 is C 4 -C 40 Hydrocarbyl or C 6 -C 30 R can be a heteroatom-containing group, m can be 0, n can be 2, and each X can be represented by formula Ic; 20 , R 20’ , R 23 , R 23’ can be hydrogen, R 21 and R 22 Each can be hydrogen or hydrocarbyl. In formula (I), R 4 and R 5 can be adamantanyl, R 2 and R 7 is C 4 -C 8 Hydrocarbyl or C 6 -C 20 R can be a heteroatom-containing group, m can be 0, n can be 2, and each X can be represented by formula Ic; 20 , R 20’ , R 23 , R 23’ can be hydrogen, R 21 and R 22 Each can be hydrogen or hydrocarbyl.

[0047] In formula (I), R 4 and R 5 can be adamantanyl, R 2 and R 7 can be tert-butyl, 1,1-dimethylpropyl, n-octyl, or tert-butyldimethylsilyl, m can be 0, n can be 2, and each of X can be represented by formula Ic; R 20 , R 20’ , R 23 , R 23’ can be hydrogen, R 21 and R 22Each can be hydrogen or hydrocarbyl. In any of the above exemplary embodiments of formula (I), R 21 and R 22 One of the groups can be hydrogen and the other can be C 1 -C 20 It is a hydrocarbyl. In any of the above exemplary embodiments of formula (I), R 21 and R 22 One of the groups can be hydrogen and the other can be C 1 -C 10 It is a hydrocarbyl. In any of the above exemplary embodiments of formula (I), R 21 and R 22 One of the groups can be hydrogen and the other is hydrogen, methyl or 4-methylpent-3-en-1-yl. In any of the above exemplary embodiments of formula (I), R 21 and R 22 One of the groups can be hydrogen and the other is methyl.

[0048] In any of the above exemplary embodiments of formula (I), R 21 and R 22 One of the groups can be hydrogen and the other is 4-methylpent-3-en-1-yl. In any of the above exemplary embodiments of formula (I), R 21 and R 22 can both be hydrogen.

[0049] In at least one embodiment, the catalyst compound is [ka] TIFF2025515175000006.tif71148 or more.

[0050] In at least one embodiment, one or more different catalyst compounds are present in the catalyst system. One or more different catalyst compounds can be present in the reaction zone in which the process described herein is carried out. The same activator can be used for the transition metal compound, but two different activators, such as a non-coordinating anion activator and an alumoxane, can be used in combination.

[0051] An exemplary embodiment of the industrial advancement of the present invention can also be a homogeneous solution comprising an aliphatic hydrocarbon solvent and a complex of formula (I), the concentration of the complex being 0.20% by weight or more (alternatively 0.25% by weight or more, alternatively 0.30% by weight or more, alternatively 0.35% by weight or more, alternatively 0.40% by weight or more, alternatively 0.50% by weight or more, alternatively 1.0% by weight or more, alternatively 2.0% by weight or more). Without intending to be bound by theory, it is believed that the solubility of the complex of formula (I) in an aliphatic solvent is improved when n is 2 and two X's taken together are represented by formula Ic. The solubility in an aliphatic solvent can be improved when R 4 and R 5 Substituents and / or R 2 and R 7 This can be further enhanced by the selection of the substituents. For example, both X's taken together are represented by formula Ic, such as 2-methylbut-2-ene-1,4-diyl, and R 2 and R 7 The choice of substituent, combined with octyl in complex 13, greatly increases the solubility of the complex in isohexane.

[0052] Another exemplary embodiment of the industrial advancement of the present invention is a process for producing a propylene-based polymer, comprising reacting propylene and one or more optional C olefins in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. 3 -C 40 Propylene and one or more optional C olefins are produced by contacting an olefin with a catalyst system comprising a composition of formula (I).3 -C 40 The method includes a step of polymerizing olefins to form a propylene-based polymer. Another exemplary embodiment of the industrial advancement of the present invention is a process for producing an ethylene-based polymer comprising reacting ethylene and one or more optional C olefins in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. 4 -C 40 Ethylene and one or more optional C's are produced by contacting an olefin with a catalyst system comprising a composition of formula (I). 4 -C 40 The method includes a process comprising the step of polymerizing olefins to form a propylene-based or ethylene-based polymer.

[0053] Activators and optional scavengers, co-activators and chain transfer agents US Patent Application No. 16 / 788,088 (Publication No. US2020 / 0254431) describes activators, optional scavengers, optional co-activators and optional chain transfer agents that can be used according to the industrial advancement of the present invention. In particular, useful activators are also non-aromatic hydrocarbon-soluble activator compounds, such as N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(pentafluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(heptafluoronaphthalenyl)borate], N-methyl-N-octadecyl-4-(octadecyloxy)anilinium [tetrakis(pentafluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(pentafluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(pentafluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(pentafluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(pentafluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecyl-4-(octadecyloxy) ... late], N-methyl-N-octadecyl-4-(octadecyloxy)anilinium [tetrakis(heptafluoronaphthalenyl)borate], N,N-di(hydrogenated tallow)methylammonium [tetrakis(pentafluorophenyl)borate], N,N-di(hydrogenated tallow)methylammonium [tetrakis(heptafluoronaphthalenyl)borate], N,N-di(octadecyl)methylammonium [tetrakis(pentafluorophenyl)borate] )borate], N,N-di(octadecyl)methylammonium [tetrakis(heptafluoronaphthalenyl)borate], N,N-di(hexadecyl)methylammonium [tetrakis(pentafluorophenyl)borate], N,N-di(hexadecyl)methylammonium [tetrakis(heptafluoronaphthalenyl)borate], N-octadecyl-N-hexadecylmethylammonium [tetrakis(pentafluorophenyl)borate No. PCT / US2020 / 044865 (publication no. WO2021 / 086467), U.S. Patent Application No. 16 / 394,174 (published as US2019 / 0330394), and PCT Application No. PCT / US2019 / 029056 (published as WO2019 / 210026), which describes N-octadecyl-N-hexadecylmethylammonium [tetrakis(heptafluoronaphthalenyl)borate] and N-octadecyl-N-hexadecylmethylammonium [tetrakis(heptafluoronaphthalenyl)borate].

[0054] It is preferred to use an activator that is soluble in non-aromatic hydrocarbon solvents, but activators that are poorly soluble or insoluble in non-aromatic hydrocarbon solvents can be used. If used, these activators can be fed to the reactor by slurry or as a solid. Particularly useful activators in this class include triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, and the like.

[0055] A typical activator to catalyst ratio is about 1:1 molar ratio. Alternative preferred ranges include 0.1:1 to 100:1, alternatively 0.5:1 to 200:1, alternatively 1:1 to 500:1, alternatively 1:1 to 1000:1. A particularly useful range is 0.5:1 to 10:1, preferably 1:1 to 1:10. Particularly useful optional scavengers or coactivators or chain transfer agents include, for example, trialkylaluminums, such as triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and dialkylzincs, such as diethylzinc. Additionally, toluene-free hydrocarbon-soluble alumoxanes and modified alumoxanes may be used, including trimethylaluminum "free" alumoxanes.

[0056] Moreover, one skilled in the art can select suitable known activators and optional scavengers or co-activators or chain transfer agents for his or her particular purpose without undue experimentation. Combinations of multiple activators can be used. Similarly, combinations of multiple optional scavengers or co-activators or chain transfer agents may be used.

[0057] solvent Although it is possible to use the catalyst components of the present industrial advancement with aromatic solvents such as toluene, preferably the catalyst components are not present when the catalyst components are used in a polymerization process. Solvents useful for dissolving the catalyst compound, activator compound, or for combining the catalyst compound and activator, and / or for introducing the catalyst system or any of its components into the reactor, and / or for use in a polymerization process include aliphatic hydrocarbon solvents, including, but not limited to, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or combinations thereof. Preferred solvents can include normal paraffins (e.g., Norpar™ solvents available from ExxonMobil Chemical Company, Houston, TX), isoparaffinic solvents (e.g., Isopar™ solvents available from ExxonMobil Chemical Company, Houston, TX), non-aromatic cyclic solvents (e.g., Nappar™ solvents available from ExxonMobil Chemical Company, Houston, TX), and combinations thereof.

[0058] Preferably, the aliphatic hydrocarbon solvent is C 4 ~C 10 Linear, branched or cyclic alkanes, alternatively C 5 ~C 8 It is selected from linear, branched or cyclic alkanes. Preferably, the aliphatic hydrocarbon solvent is substantially free of all aromatic solvents. Preferably, the solvent is substantially free of toluene. By free of all aromatic solvents such as toluene, it is meant that the solvent is substantially free of aromatic solvents (e.g., present at zero mol%, alternatively present at less than 1 mol%), and preferably the polymerization reaction and / or the resulting polymer does not contain "detectable aromatic hydrocarbon solvents" such as toluene. Preferred aliphatic hydrocarbon solvents include isohexane, cyclohexane, methylcyclohexane, pentane, isopentane, heptane, and combinations thereof, as well as commercially available solvent mixtures such as Nappar6™ and IsoparE™, however, one of ordinary skill in the art can select other suitable non-aromatic hydrocarbon solvents without undue experimentation. Highly preferred aliphatic hydrocarbon solvents include isohexane, methylcyclohexane, and commercially available solvent mixtures such as Nappar 6™ and Isopar E™. For testing the solubility of compounds, preferred solvents include isohexane and methylcyclohexane.

[0059] Optional Support Material In an embodiment of the present specification, the catalyst system may include an inert support material. The support material can be a porous support material, such as talc and inorganic oxides. U.S. Patent Application No. 16 / 788,088 (Publication No. US2020 / 0254431) describes optional support materials that can be used according to the industrial advancement of the present invention. Furthermore, a person skilled in the art can select a suitable known support for his or her particular purpose without undue experimentation.

[0060] Polymerization method The present disclosure relates to a polymerizable composition comprising a monomer (e.g., ethylene; propylene) and, optionally, one or more comonomers (e.g., C 2 -C 20 Alpha Olefin, C 4 -C 40 Cyclic olefins, C 5 -C 20 The present invention relates to a polymerization process in which a non-conjugated diene (non-conjugated diene) is contacted with a catalyst system comprising an activator and at least one catalyst compound as described above. The catalyst compound and activator may be combined in any order. The catalyst compound and activator may be combined prior to contacting with the monomer. Alternatively, the catalyst compound and activator may be introduced separately into the polymerization reactor, in which case they are subsequently reacted to form the active catalyst. U.S. Patent Application No. 16 / 788,088 (Publication No. US2020 / 0254431) describes monomers that can be used in accordance with the industrial advancement of the present invention and describes polymerization methods that can be used in accordance with the industrial advancement of the present invention. Additionally, catalysts that are highly soluble in aliphatic hydrocarbon solvents may be used as trim catalysts in known polymerization processes, for example, as described in WO2015 / 123177 and WO2020 / 092587.

[0061] Blends and Films The polymers produced by the industrial advances of the present invention can be used to make the blends and films described in U.S. Patent Application No. 16 / 788,088 (Application No. US2020 / 0254431) without undue experimentation. EXAMPLES

[0062] General Synthesis Considerations 2-Bromoiodobenzene (Millipore Sigma), cesium carbonate (Millipore Sigma), 2,6-dibromopyridine (Millipore Sigma), diisobutylaluminum hydride (Millipore Sigma), ethyl isobutyrate (Fisher Scientific), hexane (Millipore Sigma), ethylaluminum dichloride (Millipore Sigma), hydrochloric acid (Fisher Scientific), iodine (Millipore Sigma), isoprene (Millipore Sigma), 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Millipore Sigma), lithium diisopropylamide (Millipore Sigma), iodooctane (Fisher Scientific), magnesium powder (Strem Chemicals), methanesulfonyl chloride (Millipore Sigma), methanol (Millipore Sigma), methylmagnesium bromide (Millipore Sigma), 1-methyl-2-pyrrolidinone (Millipore Sigma), Pd / C (5 wt% Pd) (Millipore Sigma), potassium carbonate (Strem Chemicals), sodium bicarbonate (Fisher Scientific), sodium bromide (Millipore Sigma), sodium chloride (Fisher Scientific), sodium sulfate (Fisher Scientific), sodium thiosulfate (Millipore Sigma), tetrakis(triphenylphosphine)palladium(0) (Millipore Sigma), tert-pentylphenol (Millipore Sigma), triethylamine (Millipore Sigma), and zirconium(IV) chloride (Strem Chemicals) were used as received. Celite (Millipore Sigma) and molecular sieves (Fisher Scientific) were dried at 250 °C under high vacuum for >2 days before use. 6- Benzene (Cambridge Isotope Laboratories), dichloromethane (Millipore Sigma), d 2 -Dichloromethane (Cambridge Isotope Laboratories), diethyl ether (Millipore Sigma), 1,2-dimethoxyethane (Millipore Sigma), pentane (Millipore Sigma), tetrahydrofuran (Millipore Sigma), and toluene (Millipore Sigma) were sparged with nitrogen for >30 min and dried over activated 3 Å molecular sieves before use. Isohexane was obtained in-house and dried over 3 Å molecular sieves before use. All other reagents were purchased from commercial suppliers (Millipore Sigma, Fisher Scientific, Strem Chemicals, or Oakwood Chemical) and used as received unless otherwise stated.

[0063] The tetrahydrofuran adduct of magnesium-butadiene was prepared as described in [Organometallics 1982, v.1, pp. 388-396]. A 0.5 M solution of n-heptylmagnesium chloride in THF was synthesized from n-heptyl chloride (Sigma-Aldrich) and magnesium turnings in THF by the general synthetic protocol for the synthesis of Grignard reagents. 2-(1-adamantanyl)-4-(tert-butyl)phenol was prepared as described in Org. Lett. 2015, v.17, pg. 2242. Lithium diisopropylamide (LDA) was prepared as described in Org. Synth. 1986, v.64, pg. 68. 2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) and dimethylzirconium[2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)] (complex 14) were prepared as described in U.S. Patent Application Publication No. US2020 / 0255553. Dimethylzirconium[2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-olate)] (complex 8) was prepared as described in co-pending U.S. Provisional Application No. 63 / 338164.

[0064] [ka]

[0065] 1 H and 13 C{ 1 H}NMR spectra were recorded using at least a 400 MHz spectrometer (e.g., a Bruker Avance NEO 400 MHz spectrometer) using 1-10% solutions in deuterated solvents. 1 H and 13 The chemical shift of C corresponds to the residual deuterated solvent. 1 H or13 Based on C resonance.

[0066] All reactions were carried out in a nitrogen-filled dry box unless otherwise specified. Room temperature is 25° C. unless otherwise specified.

[0067] Synthesis of dichlorozirconium [2',2''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate] (complex 1) [ka] To a pre-cooled stirred suspension of tetrakis(dimethylamido)zirconium(IV) (0.937 g, 3.50 mmol, 1 equiv) in 1,2-dimethoxyethane (10 mL) was added zirconium(IV) chloride (0.812 g, 3.48 mmol) along with additional 1,2-dimethoxyethane (1 mL). The reaction was stirred at room temperature for 19.5 hours. Stirring was stopped and the reaction contents were allowed to settle. The supernatant was collected and concentrated under a stream of nitrogen. The resulting solid was washed with pentane (10 mL). The pentane washed solid was concentrated under high vacuum to give the 1,2-dimethoxyethane adduct of bis(dimethylamido)zirconium dichloride as a white solid (1.94 g, 81% yield). 1 H NMR (400 MHz, CD 2 Cl 2): δ 3.94 (s, 4H), 3.63 (s, 6H), 3.11 (s, 12H). To a stirred solution of bis(dimethylamido)zirconium dichloride 1,2-dimethoxyethane adduct (0.178 g, 0.524 mmol, 1 equiv) in toluene (20 mL) was slowly added a solution of 2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) (0.417 g, 0.524 mmol) in toluene (20 mL). The reaction was stirred and heated to 70 °C for 15 h. Upon cooling, the reaction was concentrated under a stream of nitrogen. The residue was then concentrated under high vacuum at 70 °C to give the product as a white solid (0.441 g, 88% yield). 1 H NMR (400 MHz, CD 2 Cl 2 ): δ 7.86 (t, 1H, J = 7.8 Hz), 7.65 (td, 2H, J = 7.6, 1.4 Hz), 7.46 (td, 2H, J = 7.6, 1.3 Hz), 7.35 (dd, 2H, J = 7.8, 1.2 Hz), 7.27 (d, 2H, J = 7.8 Hz), 7.25-7.20 (m, 4H), 6.91 (d, 2H, J = 2.5 Hz), 2.18-2.08 (m, 6H), 2.09-1.97 (m, 12H), 1.86 (br d, 6H, J = 12.0 Hz), 1.71 (br d, 6H, J = 12.0 Hz), 1.25 (s, 18H).

[0068] Synthesis of (2-butene-1,4-diyl)zirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate] (complex 2) [ka] To a stirred suspension of magnesium-butadiene tetrahydrofuran adduct (0.048 g, 0.22 mmol, 5.0 equiv.) in diethyl ether (5 mL) was added a solution of dichlorozirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)] (complex 1) (0.041 g, 0.043 mmol) in diethyl ether (5 mL). The reaction was stirred at 35° C. for 24 h. The reaction was filtered over Celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give an orange solid (0.023 g, 57% yield). The solid was mixed with pentane (2 mL) and the mixture was filtered. The filtrate was concentrated under a stream of nitrogen and then under high vacuum. The residue was mixed with hexane (2 mL) and heated to reflux until the solid residue was completely dissolved. The solution was then slowly cooled to room temperature, producing small yellow crystals that were used for structural confirmation by X-ray diffraction. 1 H NMR (400 MHz, C 6 D 6 ): δ 7.39 (d, 2H, J = 2.6 Hz), 7.26-7.17 (m, 5H), 7.14-7.08 (m, 3H), 7.03 (d, 2H, J = 2.6 Hz), 6.58 (s, 2H), 5.65-5.51 (br s, 2H), 2.67-1.54 (br m, 34H), 1.30 (s, 18H).

[0069] Synthesis of (2-methyl-2-butene-1,4-diyl)zirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate] (complex 3) [ka] To a stirred suspension of activated magnesium powder (0.007 g, 0.3 mmol, 5.6 equiv.) in diethyl ether (2 mL) was added a solution of dichlorozirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)] (complex 1) (0.049 g, 0.051 mmol) in tetrahydrofuran (5 mL). Isoprene (0.05 mL, 0.5 mmol, 9.8 equiv.) was then added. The reaction was stirred at room temperature for 24 h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane (10 mL) and filtered over Celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give an orange solid (0.036 g, 73% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ 7.42 (d, 1H, J = 2.7 Hz), 7.38-7.33 (m, 2H), 7.27-7.17 (m, 4H), 7.14-7.06 (m, 3H), 7.05 (d, 1H, J = 2.6 Hz), 7.00 (d, 1H, J = 2.5 Hz), 6.64-6.51 (m, 3H), 5.50 (t, 1H, J = 11.7 Hz), 2.93 (t, 1H, J = 10.4 Hz), 2.5 (d, 1H, J = 8.8 Hz), 2.29-2.15 (m, 6H), 2.15-2.08 (m, 9H), 2.05-1.96 (m, 3H), 1.91-1.73 (m, 15H), 1.33 (s, 9H), 1.27 (s, 9H), 1.09 (d, 1H, J = 9.9 Hz), 1.01 (t, 1H, J = 11.3 Hz).

[0070] Synthesis of ethyl 2,2-dimethyldecanoate (A) [ka] To a stirred solution of lithium diisopropylamide (9.93 g, 92.7 mmol, 1.06 equiv) in tetrahydrofuran (90 mL) at -78°C was added ethyl isobutyrate (11.8 mL, 87.9 mmol) dropwise over 5 min. The reaction was stirred at -78°C for 100 min. Iodooctane (16.3 mL, 90.5 mmol, 1.03 equiv) was then added. The reaction was allowed to warm slowly to room temperature and stirred overnight. The reaction was transferred to a fume hood and quenched with water (10 mL). Additional water (100 mL) and diethyl ether (100 mL) were then added to the reaction. The contents were poured into a separatory funnel and the organic layer was extracted. The aqueous phase was further extracted with diethyl ether (2 x 50 mL). The combined organic extracts were washed with brine, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated in vacuo to give the crude product, which was purified by silica gel column chromatography (100% isohexane, then 5% diethyl ether in isohexane) to give the product as a clear, colorless oil (17.8 g, 88% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ 3.99 (q, 2H, J = 7.1 Hz), 1.59-1.52 (m, 2H), 1.36-1.22 (m, 12H), 1.21 (s, 6H), 0.97 (t, 3H, J = 7.1 Hz), 0.90 (t, 3H, J = 6.9 Hz).

[0071] Synthesis of 2,2-dimethyldodecanol (B) [ka] To a pre-cooled stirred solution of ethyl 2,2-dimethyldecanoate (A) (17.8 g, 77.9 mmol) in dichloromethane (450 mL) was added diisobutylaluminum hydride (29.0 mL, 163 mmol, 2.09 equiv). The reaction was stirred at room temperature for 18.5 h. The reaction was transferred to a fume hood, quenched with wet methanol (100 mL) and diluted with brine (100 mL). The resulting mixture was filtered over a plastic fritted funnel and the filtered solid was further extracted with diethyl ether (50 mL). Additional diethyl ether (100 mL) was added to the filtrate. The filtrate was poured into a separatory funnel and the organic layer was collected. The aqueous phase was further extracted with diethyl ether (2×100 mL). The combined organic extracts were dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated in vacuo. The resulting crude product was filtered over a thick pad (15-20 cm thick) of silica packed with pentane and the first fraction was extracted with pentane (300 mL). In a separate flask, the material remaining on the silica gel was extracted with 20% diethyl ether in pentane (500 mL). The second fraction was concentrated in vacuo to give the product fraction (11.0 g). The first fraction contained iodooctane contaminant (1:0.14 product:iodooctane) and was therefore further purified by silica gel column chromatography. The pure fraction from this column was combined with the pure second fraction from the filtration through silica to give the product as a clear, colorless oil (12.88 g, 88% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ 3.10 (d, 2H, J = 5.7 Hz), 1.38-1.15 (m, 14H), 0.95-0.89 (m, 3H), 0.82 (s, 6H), 0.65 (t, 1H, J = 5.7 Hz).

[0072] Synthesis of 2,2-dimethyldecyl methanesulfonate (C) [ka] To a stirred solution of 2,2-dimethyldodecanol (B) (4.71 g, 25.3 mmol) and triethylamine (5.3 mL, 38 mmol, 1.5 equiv.) in dichloromethane (150 mL) was added methanesulfonyl chloride (2.2 mL, 28 mmol, 1.1 equiv.) over approximately 30 seconds. The reaction, a light orange solution, was stirred at room temperature for 19 hours. The reaction was transferred to a fume hood and poured into ice water in a separatory funnel. The mixture was shaken and the organic layer was collected. The aqueous layer was further extracted with dichloromethane (100 mL). The combined dichloromethane extracts were washed with aqueous hydrochloric acid (50 mL, 1 M), then saturated aqueous sodium bicarbonate (50 mL), then brine. The organic extract was dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo to give the product as an orange-brown oil (5.32 g, 79% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ 3.65 (s, 2H), 2.36-2.21 (m, 3H), 1.42-1.00 (m, 14H), 0.95-0.86 (m, 3H), 0.74 (s, 6H).

[0073] Synthesis of 1-bromo-2,2-dimethyldecane (D) [ka] A mixture of 2,2-dimethyldecyl methanesulfonate (C) (1.00 g, 3.80 mmol) and anhydrous sodium bromide (1.17 g, 11.4 mmol, 3 equiv.) was stirred under high vacuum for 1 h. To this mixture was then added 1-methyl-2-pyrrolidinone (8 mL). The resulting solution was stirred and heated to 140° C. for 2 h. The reaction was allowed to cool to room temperature. The reaction was then transferred to a fume hood and partitioned between water (100 mL) and pentane (50 mL). The aqueous layer was discarded and the pentane extract was washed with aqueous sodium thiosulfate (50 mL). The pentane extract was collected, dried over anhydrous potassium carbonate, and filtered. The filtrate was concentrated in vacuo to give the product as an orange oil (0.728 g, 76% yield). 1H NMR (400 MHz, C 6 D 6 ): δ 2.98 (s, 2H), 1.38-1.14 (m, 12H), 1.13-1.00 (m, 2H), 0.93 (t, 3H, J = 6.9 Hz), 0.82 (s, 6H).

[0074] Synthesis of 2,2-dimethyldecylmagnesium bromide (E) [ka] To a grey suspension of magnesium powder (0.390 g, 16.0 mmol, 2 equiv.) in diethyl ether (20 mL) was added iodine (0.102 g, 0.05 equiv.). The reaction was stirred until the brown suspension returned to a grey suspension. 1-Bromo-2,2-dimethyldecane (D) (2.00 g, 8.02 mmol) was then added. The reaction was stirred at room temperature for 5 h. The resulting suspension was filtered over Celite. Titration of the filtrate indicated a concentration of 0.13 M. 1 H NMR also revealed that 9,9,12,12-tetramethyleicosane had formed (see procedure below). The solution was used as is without further characterization.

[0075] Synthesis of 9,9,12,12-tetramethyleicosane (F) [ka] To a stirred suspension of magnesium powder (0.360 g, 14.8 mmol, 19.1 equiv.) in diethyl ether (50 mL) was rapidly added a solution of 1-bromo-2,2-dimethyldecane (D) (0.193 g, 0.774 mmol) in diethyl ether (10 mL). The reaction was stirred overnight at room temperature. The reaction was filtered over Celite. A sample of the filtrate was titrated with iodine in tetrahydrofuran / lithium chloride to confirm the absence of active Grignard species as determined by no loss of color. 1 H NMR (400 MHz, C 6 D 6): δ 1.37-1.21 (m, 16H), 0.96-0.87 (m, 9H).

[0076] Synthesis of methyl-(2,2-dimethyldecyl)zirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate] (complex 4) [ka] To a stirred solution of dichlorozirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)] (complex 1) (0.070 g, 0.073 mmol) in diethyl ether was added methylmagnesium bromide (0.02 mL, 3.0 M in diethyl ether, 0.07 mmol, 0.8 equiv). The reaction was stirred and heated to reflux for 2 h. A solution of 2,2-dimethyldecylmagnesium bromide (E) in diethyl ether (0.56 mL, 0.13 M in diethyl ether, 0.073 mmol, 1 equiv) and toluene (5 mL) were then added. The reaction was stirred and heated to 90° C. for 66 h. Additional methylmagnesium bromide was then added and the reaction was heated to 105° C. for 1.5 h. The reaction was concentrated under a stream of nitrogen. The resulting residue was extracted with pentane (5 mL) and filtered over Celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum. The resulting residue was dissolved in pentane (2 mL) and cooled to -35°C. The resulting mixture was filtered over Celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give the product containing 9,9,12,12-tetramethyleicosane (1.42 equiv.) as an impurity. 1 H NMR (400 MHz, C 6 D 6): δ 7.59 (d, 1H, J = 2.6 Hz), 7.55 (d, 1H, J = 2.7 Hz), 7.43 (dd, 1H, J = 7.7, 1.1 Hz), 7.31 (td, 1H, J = 7.6, 1.3 Hz), 7.21 (dd, 2H, J = 7.7, 1.4 Hz), 7.12-6.99 (m, 5H), 6.86 (dd, 1H, J = 7.5, 1.6 Hz), 6.46-6.40 (m, 2H), 6.29 (dd, 1H, J = 6.4, 2.5 Hz), 2.70-2.61 (m, 3H), 2.58-2.52 (m, 3H), 2.51-2.45 (m, 3H), 2.39-2.32 (m, 3H), 2.29-2.22 (m, 6H), 2.12-2.03 (m, 6H), 1.94-1.82 (m, 6H), 1.73 (d, 1H, J = 12.6 Hz), 1.40-0.84 (m, 41H), 0.04 (s, 3H), -1.01 (d, 1H, J = 12.7 Hz).

[0077] Synthesis of 2-(adamantan-1-yl)-4-(tert-pentyl)phenol (G) [ka] To a solution of 39.5 g (241 mmol) of tert-pentylphenol in dichloromethane (240 ml) was added 36.7 g (241 mmol) of adamantan-1-ol. 14.5 ml of sulfuric acid was then added dropwise over 30 min to the resulting solution. The resulting suspension was stirred at room temperature for 30 min and then carefully poured into 300 ml of crushed ice containing 50 ml of saturated aqueous ammonia. The resulting mixture was extracted with dichloromethane (3x100 ml) and the combined organic extracts were diluted with 5% NaHCO 3 Wash with Na 2 SO 4 The mixture was dried at 37° C. and then evaporated to dryness. The residue was recrystallized from n-hexane. Yield 43.2 g (60%) of a white solid. 1 H NMR (CDCl 3, 400 MHz): δ 7.21 (d, J = 2.3 Hz, 1H), 7.03 (dd, J = 8.2, 2.3 Hz, 1H), 6.58 (d, J = 8.2 Hz, 1H), 4.60 (s, 1H), 2.13 - 2.19 (m, 6H), 2.12 (br.s, 3H), 1.79 - 1.85 (m, 6H), 1.64 (q, J = 7.5 Hz, 2H), 1.29 (s, 6H), 0.73 (t, J = 7.5 Hz, 3H). 13 C NMR (CDCl 3 , 100 MHz): δ 151.8, 141.4, 135.4, 124.6, 123.9, 116.1, 40.6, 37.5, 37.1, 37.0, 36.8, 29.1, 28.6, 9.2.

[0078] Synthesis of 2-(adamantan-1-yl)-6-bromo-4-(tert-pentyl)phenol (H) [ka] To a solution of 43.9 g (147 mmol) of 2-(adamantan-1-yl)-4-(tert-pentyl)phenol (G) in chloroform (400 ml) was added dropwise a solution of 7.53 ml (147 mmol) of bromine in chloroform (200 ml) at room temperature for 30 minutes. The resulting mixture was diluted with 400 ml of water. The resulting mixture was extracted with dichloromethane (3×100 ml) and the combined organic extracts were diluted with 5% NaHCO 3 Wash with Na 2 SO 4 The mixture was dried at 40° C. and then evaporated to dryness. Yield 55.4 g (almost quantitative) of a white solid. 1 H NMR (CDCl 3, 400 MHz): δ 7.28 (d, J = 2.2 Hz, 1H), 7.14 (d, J = 2.2 Hz, 1H), 5.67 (s, 1H), 2.13 - 2.17 (m, 6H), 2.11 (br.s, 3H), 1.78 - 1.84 (m, 6H), 1.62 (q, J = 7.5 Hz, 2H), 1.27 (s, 6H), 0.72 (t, J = 7.5 Hz, 3H). 13 C NMR (CDCl 3 , 100 MHz): δ 147.9, 142.1, 136.9, 126.7, 124.2, 112.2, 40.3, 37.63, 37.60, 37.0, 36.9, 29.0, 28.5, 9.2.

[0079] Synthesis of 1-(3-bromo-2-(methoxymethoxy)-5-(tert-pentyl)phenyl)adamantane (I) [ka] To a solution of 55.4 g (147 mmol) of 2-(adamantan-1-yl)-6-bromo-4-(tert-pentyl)phenol (H) in THF (700 ml) was added 6.35 g (159 mmol, 60% by weight in mineral oil) of sodium hydride in small portions at room temperature. To the resulting suspension was added 12.1 ml (159 mmol) of methoxymethyl chloride dropwise at room temperature for 10 min. The resulting mixture was stirred overnight and then poured into 1000 ml of water. The resulting mixture was extracted with dichloromethane (3×300 ml) and the combined organic extracts were washed with 5% NaHCO 3 Wash with Na 2 SO 4 The mixture was dried at 40° C. and then evaporated to dryness. Yield 61.8 g (quantitative) of a white solid. 1 H NMR (CDCl 3, 400 MHz): δ7.32 (d, J = 2.4 Hz, 1H), 7.17 (d, J = 2.4 Hz, 1H), 5.22 (s, 2H), 3.70 (s, 3H), 2.04 - 2.14 (m, 9H), 1.72 - 1.80 (m, 6H), 1.58 (q, J = 7.4 Hz, 2H), 1.23 (s, 6H), 0.68 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl 3 , 100 MHz): δ 150.7, 146.0, 144.3, 129.1, 124.4, 117.5, 99.5, 57.8, 41.4, 38.0, 37.8, 36.9, 36.8, 29.1, 28.3, 9.1.

[0080] Synthesis of 2-(3-(adamantan-1-yl)-2-(methoxymethoxy)-5-(tert-pentyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (J) [ka] A solution of 61.8 g (147 mmol) of 1-(3-bromo-2-(methoxymethoxy)-5-(tert-pentyl)phenyl)adamantane (I) in dry THF (1,000 ml) was added to 70.1 ml (176 mmol) of 2.5 M hexane at -80°C. n BuLi was added dropwise over 20 min. The reaction mixture was stirred at this temperature for 1 h, then 45.3 ml (220 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The resulting suspension was stirred at room temperature for 1 h, then poured into 300 ml of water. The resulting mixture was extracted with dichloromethane (3×300 ml) and the combined organic extracts were washed with Na 2 SO 4 The mixture was dried at 40° C. and then evaporated to dryness. Yield 69.2 g (quantitative) of a colorless viscous oil. 1 H NMR (CDCl 3, 400 MHz): δ 7.45 (d, J = 2.6 Hz, 1H), 7.33 (d, J = 2.6 Hz, 1H), 5.16 (s, 2H), 3.58 (s, 3H), 2.13 - 2.18 (m, 6H), 2.07 (br.s, 3H), 1.73 - 1.83 (m, 6H), 1.62 (q, J = 7.4 Hz, 2H), 1.35 (s, 12H), 1.27 (s, 6H), 0.69 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl 3 , 100 MHz): δ 159.6, 143.0, 140.4, 131.3, 128.0, 100.9, 83.5, 57.7, 41.3, 37.6, 37.3, 37.1, 36.9, 29.2, 28.4, 24.8, 9.2.

[0081] Synthesis of 1-(2'-bromo-2-(methoxymethoxy)-5-(tert-pentyl)-[1,1'-biphenyl]-3-yl)adamantane (K) [ka] To a solution of 34.5 g (73.5 mmol) of 2-(3-(adamantan-1-yl)-2-(methoxymethoxy)-5-(tert-pentyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (J) in 1,4-dioxane (200 ml) was added successively 20.9 g (73.5 mmol) of 2-bromoiodobenzene, 60.1 g (184 mmol) of cesium carbonate and 100 ml of water. The resulting mixture was purged with argon for 10 min and then 4.25 g (3.69 mmol) of Pd(PPh 3 ) 4 The mixture was stirred at 100° C. for 12 hours, then cooled to room temperature and diluted with 100 ml of water. The resulting mixture was extracted with dichloromethane (3×100 ml) and the combined organic extracts were washed with Na 2 SO 4The mixture was dried at 40° C. and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane=10:1, by volume). Yield 19.7 g (54%) of a white solid. 1 H NMR (CDCl 3 , 400 MHz): δ7.68 (d, J = 7.8 Hz, 1H), 7.42 (dd, J = 7.6, 1.5 Hz, 1H), 7.35 (t, J = 7.1 Hz, 1H), 7.29 (d, J = 2.3 Hz, 1H), 7.20 (dt, J = 7.9, 1.5 Hz, 1H), 7.02 (d, J = 2.3 Hz, 1H), 4.54-4.55 (m, 1H), 4.41 - 4.42 (m, 1H), 3.21 (s, 3H), 2.17 - 2.21 (m, 6H), 2.11 (br.s, 3H), 1.75 - 1.86 (m, 6H), 1.64 (dq, J = 7.5, 3.0 Hz, 2H), 1.31 (s, 3H), 1.28 (s, 3H), 0.73 (t, J = 7.5 Hz, 3H). 13 C NMR (CDCl 3 , 100 MHz): δ 151.2, 143.5, 142.0, 141.6, 133.8, 132.9, 132.4, 128.5, 127.4, 127.0, 124.5, 124.3, 98.8, 57.1, 41.4, 37.8, 37.5, 37.0, 29.2, 28.43, 28.38, 9.2.

[0082] Synthesis of 4-(adamantan-1-yl)-6-isopropoxy-2-(tert-pentyl)-6H-dibenzo[c,e][1,2]oxaborinine (L) [ka] A solution of 19.7 g (39.6 mmol) of 1-(2'-bromo-2-(methoxymethoxy)-5-(tert-pentyl)-[1,1'-biphenyl]-3-yl)adamantane (K) in dry THF (300 ml) was added to 19.0 ml (47.5 mmol) of 2.5 M hexane at -80°C. n BuLi was added dropwise over 20 min. The reaction mixture was stirred at this temperature for 1 h, then 12.1 ml (59.3 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The resulting suspension was stirred at room temperature for 1 h, then poured into 300 ml of water. The resulting mixture was extracted with dichloromethane (3×300 ml) and the combined organic extracts were washed with Na 2 SO 4 The residue was dried at 37° C. and then evaporated to dryness. To the residue, 120 ml of isopropanol was added and the resulting solution was refluxed for 2 hours. After cooling to room temperature, the formed precipitate was filtered off on a glass frit (G4), washed with 10 ml of cold isopropanol and dried in vacuum. Yield 13.6 g (77%) of a white solid. 1 H NMR (CDCl 3 , 400 MHz): δ8.19 (d, J = 8.3 Hz, 1H), 8.09 (d, J = 6.5 Hz, 1H), 8.01 (d, J = 2.0 Hz, 1H), 7.67 (dt, J = 7.6, 1.5 Hz, 1H), 7.43 (t, J = 7.3 Hz, 1H), 7.37 (d, J = 2.2 Hz, 1H), 5.27 (septet, J = 6.1 Hz, 1H), 2.28 - 2.38 (m, 6H), 2.18 (br.s, 3H), 1.83 - 1.93 (m, 6H), 1.74 (q, J = 7.4 Hz, 2H), 1.43 (d, J = 6.1 Hz, 6H), 1.40 (s, 6H), 0.76 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl 3, 100 MHz): δ148.2, 142.2, 141.0, 138.8, 133.1, 126.5, 124.6, 122.1, 118.8, 65.7, 40.8, 37.9, 37.4, 37.2, 37.0, 29.2, 28.7, 24.7, 9.3.

[0083] Synthesis of 2',2'''-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-ol) (M) [ka] To a solution of 13.6 g (30.6 mmol) of 4-(adamantan-1-yl)-6-isopropoxy-2-(tert-pentyl)-6H-dibenzo[c,e][1,2]oxaborinine (L) in 1,4-dioxane (80 ml) was added 3.55 g (15.0 mmol) of 2,6-dibromopyridine, 24.4 g (76.6 mmol) of cesium carbonate and 38 ml of water in succession. The resulting mixture was purged with argon for 10 min and then 1.77 g (1.55 mmol) of Pd(PPh 3 ) 4 The mixture was stirred at 100° C. for 12 hours, then cooled to room temperature and diluted with 50 ml of water. The resulting mixture was extracted with dichloromethane (3×50 ml) and the combined organic extracts were washed with Na 2 SO 4 The mixture was dried at 40° C. and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate=10:1, by volume). Yield 10.5 g (85%) of a mixture of two isomers as a glassy solid. 1 H NMR (CDCl 3, 400 MHz): δ 8.00 (s, 2H in A), 7.39 - 7.59 (m, 9H in A and B), 7.06 (d, J = 2.1 Hz, 2H in A and B), 7.01 (d, J = 7.6 Hz, 2H in B), 6.99 (d, J = 7.8 Hz, 2H in A), 6.88 (d, J = 2.1 Hz, 2H in B), 6.55 (d, J = 2.1 Hz, 2H in A), 6.36 (s, 2H in B), 1.91 - 2.08 (m, 18H in A and B), 1.71 (br.s, 12H in A and B), 1.49 (dq, J = 7.6, 2.5 Hz, 4H in B), 1.26 - 1.45 (m, 4H in A), 1.18 (s, 6H in B), 1.17 (s, 6H in B), 1.06 (s, 6H in A), 1.03 (s, 6H in A), 0.57 (t, J = 7.5 Hz, 6H in B), 0.42 (t, J = 7.5 Hz, 6H in A). 13 C NMR (CDCl 3 , 100 MHz, signals due to minor isomers are marked with *): δ 157.8, 149.9, 149.1*, 140.1*, 140.0*, 139.9, 139.5, 137.8, 137.2, 137.1*, 136.8, 136.1*, 131.8, 130.9, 130.5*, 129.6, 129.0*, 128.9, 128.5*, 127.9*, 127.7, 126.8, 126.3*, 123.6, 122.5, 122.1*, 40.5, 40.4*, 37.3*, 37.2, 37.0, 36.99*, 36.92*, 36.87, 29.12, 29.09*, 28.49, 28.44, 28.41*, 28.3, 9.12*, 9.07.

[0084] Synthesis of dimethylzirconium [2',2''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-olate] (complex 5) [ka] To a suspension of 707 mg (3.03 mmol) of zirconium tetrachloride in dry toluene (350 ml) at -30°C was added 4.71 ml (13.5 mmol) of 2.9 M MeMgBr in diethyl ether in one portion via syringe. To the resulting suspension was immediately added 2.50 g (3.03 mmol) of 2',2'''-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-ol) (M) in one portion. The reaction mixture was stirred at room temperature for 3 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 100 ml of toluene and the combined organic extracts were filtered through a thin pad of Celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 10 ml of n-hexane and the resulting precipitate was filtered off (G3), washed twice with 10 ml of n-hexane and then dried in vacuum. Yield 2.66 g (93%) of a beige solid. Elemental analysis: C 61 H 73 ZrNO 2 Calculated values: C, 77.66; H, 7.80; N, 1.48. Found values: C 77.88; H, 8.01; N 1.26. 1 H NMR (C 6 D 6 , 400 MHz): δ 7.48 (d, J = 2.4 Hz, 2H), 7.20 (dd, J = 7.2, 1.1 Hz, 2H), 6.95 - 7.13 (m, 8H), 6.54 (dd, J = 8.3, 7.2 Hz, 1H), 6.41 (d, J = 7.9 Hz, 2H), 2.52 - 2.61 (m, 6H), 2.38 - 2.47 (m, 6H), 2.19 (br.s, 6H), 1.95 - 2.04 (m, 6H), 1.80 - 1.89 (m, 6H), 1.64 (dq, J = 7.5, 2.3 Hz, 4H), 1.31 (s, 6H), 1.29 (s, 6H), 0.76 (t, J = 7.5 Hz, 6H), 0.12 (s, 6H). 13 C NMR (C 6 D 6, 100 MHz): δ 159.1, 158.3, 143.8, 139.4, 138.7, 138.0, 133.6, 133.3, 133.1, 131.5, 131.2, 127.9, 126.5, 125.1, 124.5, 42.9, 42.0, 38.5, 38.0, 37.91, 37.85, 30.0, 29.3, 29.2, 9.9.

[0085] Synthesis of dimethylzirconium [2',2''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-olate] (complex 6) [ka] To a stirred solution of dimethylzirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-olate)] (complex 5) (0.236 g, 0.250 mmol) in toluene (15 mL) was added a solution of ethylaluminum dichloride (0.55 mL, 1.01 M in hexanes, 0.56 mmol, 2.2 equiv). The reaction was stirred and heated to 60° C. for 3 h. Upon cooling, the reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in hexanes (10 mL) and filtered on a plastic fritted funnel. The filtered solid was further washed with hexanes (5 mL). The solid was collected and concentrated under high vacuum to give the product as a light grey solid (0.226 g, 91% yield). 1 H NMR (400 MHz, C 6 D 6): δ 7.50-7.44 (m, 2H), 7.26-7.13 (m, 6H), 7.09-7.02 (m, 2H), 7.01-6.94 (m, 2H), 6.52-6.46 (m, 1H), 6.42-6.33 (m, 2H), 2.52-2.40 (m, 6H), 2.40-2.28 (m, 6H), 2.23-2.03 (m, 12H), 1.88-1.77 (m, 6H), 1.67-1.55 (m, 4H), 1.31-1.20 (m, 12H), 0.79-0.70 (m, 6H).

[0086] Synthesis of (2-methylbut-2-ene-1,4-diyl)zirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-olate] (complex 7) [ka] To a stirred suspension of activated magnesium powder (0.015 g, 0.62 mmol, 6.1 equiv.) in diethyl ether (3 mL) was added a solution of dichlorozirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-olate)] (complex 6) (0.099 g, 0.10 mmol) in tetrahydrofuran (3 mL). Isoprene (0.08 mL, 0.8 mmol, 8 equiv.) was then added. The reaction was stirred at room temperature for 2.5 h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane (15 mL) and filtered over Celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give the product (0.049 g, 48% yield) containing hexane (0.42 equiv.) as an orange solid. 1 H NMR (400 MHz, C 6 D 6): δ 7.38-7.32 (m, 2H), 7.27 (d, 1H, J = 2.6 Hz), 7.26-7.08 (m, 7H), 6.95 (d, 1H, J = 2.6 Hz), 6.91 (d, 1H, J = 2.5 Hz), 6.73-6.57 (m, 3H), 5.49 (t, 1H, J = 11.7 Hz), 2.93 (t, 1H, J = 10.6 Hz), 2.61 (d, 1H, J = 8.6 Hz), 2.30-2.15 (m, 6H), 2.15-2.06 (m, 9H), 2.04-1.95 (m, 3H), 1.92-1.74 (m, 15H), 1.66-1.52 (m, 4H), 1.30 (s, 3H), 1.28 (s, 3H), 1.26 (s, 3H), 1.23 (s, 3H), 1.09 (d, 1H, J = 9.1 Hz), 1.02 (t, 1H, J = 11.3 Hz), 0.74 (t, 3H, J = 7.4 Hz), 0.66 (t, 3H, J = 7.4 Hz).

[0087] Synthesis of dichlorozirconium [2',2''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-olate] (complex 9) [ka] To a stirred solution of dimethylzirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-olate)] (complex 8) (0.272 g, 0.264 mmol) in toluene (15 mL) was added a solution of ethylaluminum dichloride (0.58 mL, 1.01 M in hexanes, 0.59 mmol, 2.2 equiv). The reaction was stirred and heated to 60° C. for 5 h. Upon cooling, the reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in hexanes (10 mL) and filtered on a plastic fritted funnel. The filtered solid was further washed with hexanes (5 mL). The solid was collected and concentrated under high vacuum to give the product as a light grey solid (0.262 g, 92% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ 7.74-7.69 (m, 2H), 7.28-7.12 (m, 8H), 7.08-7.03 (m, 2H), 6.49-6.43 (m, 1H), 6.39-6.30 (m, 2H), 2.53-2.41 (m, 6H), 2.41-2.31 (m, 6H), 2.21-2.12 (m, 6H), 2.11-2.00 (m, 6H), 1.86-1.73 (m, 6H), 1.01-0.95 (m, 18H), 0.30-0.21 (m, 12H).

[0088] Synthesis of (2-methylbut-2-ene-1,4-diyl)zirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-olate] (complex 10) [ka] To a stirred suspension of activated magnesium powder (0.012 g, 0.49 mmol, 5.3 equiv.) in diethyl ether (3 mL) was added a solution of dichlorozirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-olate)] (complex 9) (0.100 g, 0.093 mmol) in tetrahydrofuran (3 mL). Isoprene (0.07 mL, 0.7 mmol, 7.5 equiv.) was then added. The reaction was stirred at room temperature for 2 h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was washed and stirred in hexane (10 mL) and filtered over Celite. The hexane washed solid was then extracted with toluene (5 mL). The toluene extract was concentrated under a stream of nitrogen and then under high vacuum to give the product as a brown solid (0.068 g, 68% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ 7.58 (d, 1H, J = 1.8 Hz), 7.50 (d, 1H, J = 1.8 Hz), 7.33 (d, 1H, J = 6.7 Hz), 7.25-6.99 (m, 9H), 6.70-6.64 (m, 1H), 6.63-6.56 (m, 2H), 5.49 (t, 1H, J = 11.7 Hz), 2.92 (t, 1H, J = 10.7 Hz), 2.59 (d, 1H, J = 9.1 Hz), 2.31-2.16 (m, 6H), 2.15-2.04 (m, 9H), 2.03-1.95 (m, 3H), 1.91-1.69 (m, 15H), 1.13 (d, 1H, J = 8.9 Hz), 1.09-1.03 (m, 1H), 0.97 (s, 9H), 0.91 (s, 9H), 0.29 (s, 3H), 0.27 (s, 3H), 0.26 (s, 3H), 0.23 (s, 3H).

[0089] Synthesis of 1-(2-(methoxymethoxy)-5-octylphenyl)adamantane(N) [ka] To a solution of 17.1 g (56.9 mmol) of 3-(adamantan-1-yl)-4-(methoxymethoxy)benzaldehyde in THF (100 ml) at 0° C., 240 ml (120 mmol) of 0.5 M n-heptylmagnesium chloride in THF was added dropwise over 20 min. The resulting suspension was stirred at room temperature for 12 h and then poured into 300 ml of water. The resulting mixture was extracted with dichloromethane (3×200 ml) and the combined organic extracts were washed with Na 2 SO 4 The mixture was dried at 300° C. and then evaporated to dryness. The residue was transferred to a hydrogenation reactor and then dissolved in a mixture of 75 ml of methanol and 75 ml of THF. To the resulting solution, 4.0 g of Pd / C (5% by weight of Pd) was added and the reactor was pressurized with hydrogen to 270 psi. The reaction mixture was stirred at constant pressure at room temperature overnight and then depressurized. The reaction mixture was filtered through a Celite 503 pad and the filtrate was evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane=10:1→4:1, by volume). Yield 16.1 g (73%) of a yellow oil. 1 H NMR (CDCl 3 , 400 MHz): δ7.09 (d, J = 2.1 Hz, 1H), 7.06 (d, J = 8.3 Hz, 1H), 6.99 (dd, J = 8.3, 2.1 Hz, 1H), 5.24 (s, 2H), 3.56 (s, 3H), 2.56 - 2.60 (m, 2H), 2.16 - 2.19 (m, 6H), 2.12 (br.s, 3H), 1.81 - 1.85 (m, 6H), 1.59 - 1.68 (m, 2H), 1.25 - 1.40 (m, 10H), 0.93 (t, J = 7.1Hz, 3H). 13C NMR (CDCl3, 100 MHz): δ 154.5, 138.2, 135.7, 126.8, 126.3, 114.3, 94.4, 56.0, 40.7, 37.1, 36.9, 35.6, 31.9, 31.8, 29.5, 29.3, 29.1, 22.7, 14.1.

[0090] Synthesis of 2-(3-(adamantan-1-yl)-2-(methoxymethoxy)-5-octylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(O) [ka] A solution of 16.0 g (41.6 mmol) of 1-(2-(methoxymethoxy)-5-octylphenyl)adamantane (N) in diethyl ether (250 ml) was added to 25.0 ml (62.4 mmol) of 2.5 M hexane at 0° C. n BuLi was added dropwise over 20 min. The reaction mixture was stirred at room temperature for 12 h, cooled to -80°C, and then 17.0 ml (83.2 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The resulting suspension was stirred at room temperature for 1 h and then poured into 300 ml of water. The resulting mixture was extracted with dichloromethane (3 x 200 ml) and the combined organic extracts were washed with Na 2 SO 4 The mixture was dried at rt and then evaporated to dryness. Yield 20.6 g (97%) of a colorless oil. 1 H NMR (CDCl 3 , 400 MHz): δ7.36 (d, J = 2.3 Hz, 1H), 7.20 (d, J = 2.3 Hz, 1H), 5.17 (s, 2H), 3.61 (s, 3H), 2.53 - 2.57 (m, 2H), 2.15 - 2.20 (m, 6H), 2.09 (br.s, 3H), 1.74 - 1.84 (m, 6H), 1.55 - 1.64 (m, 2H), 1.37 (s, 12H), 1.24 - 1.38 (m, 10H), 0.90 (t, J = 7.1 Hz, 3H).13 C NMR (CDCl 3 , 100 MHz): δ 159.5, 140.8, 136.5, 133.5, 130.1, 100.6, 83.2, 57.4, 40.9, 36.7, 35.2, 31.5, 31.4, 29.2, 29.1, 28.9, 28.8, 24.4, 22.3, 13.7.

[0091] Synthesis of 1-(2'-bromo-2-(methoxymethoxy)-5-octyl-[1,1'-biphenyl]-3-yl)adamantane (P) [ka] To a solution of 20.5 g (40.3 mmol) of 2-(3-(adamantan-1-yl)-2-(methoxymethoxy)-5-octylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (O) in 1,4-dioxane (100 ml) was added successively 13.7 g (48.3 mmol) of 2-bromoiodobenzene, 33.0 g (100 mmol) of cesium carbonate and 50 ml of water. The resulting mixture was purged with argon for 10 min and then 2.31 g (2.00 mmol) of Pd(PPh 3 ) 4 The mixture was stirred at 100° C. for 12 hours, then cooled to room temperature and diluted with 100 ml of water. The resulting mixture was extracted with dichloromethane (3×100 ml) and the combined organic extracts were washed with Na 2 SO 4 The mixture was dried at 40° C. and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane=10:1, by volume). Yield 14.5 g (67%) of a colorless oil. 1 H NMR (CDCl 3, 400 MHz): δ7.69 (d, J = 8.0 Hz, 1H), 7.40 (d, J = 7.6 Hz, 1H), 7.36 (t, J = 7.6 Hz, 1H), 7.21 (dt, J = 8.0, 1.8 Hz, 1H), 7.16 (d, J = 1.8 Hz, 1H), 6.91 (d, J = 1.8 Hz, 1H), 4.53 - 4.54 (m, 1H), 4.45 - 4.46 (m, 1H), 3.22 (s, 3H), 2.58 - 2.62 (m, 2H), 2.19 - 2.21 (m, 6H), 2.12 (br.s, 3H), 1.78 - 1.84 (m, 6H), 1.60 - 1.69 (m, 2H), 1.25 - 1.37 (m, 10H), 0.90 - 0.92 (m, 3H). 13 C NMR (CDCl3, 100 MHz): δ151.2, 142.4, 140.9, 136.9, 134.1, 132.5, 131.9, 128.9, 128.2, 126.72, 126.69, 123.8, 98.5, 56.7, 40.9, 36.9, 36.6, 35.3, 31.5, 31.1, 29.08, 29.06, 28.9, 28.8, 22.4, 13.8.

[0092] Synthesis of 2-(3'-(adamantan-1-yl)-2'-(methoxymethoxy)-5'-octyl-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Q) [ka] A solution of 14.5 g (26.9 mmol) of 1-(2'-bromo-2-(methoxymethoxy)-5-octyl-[1,1'-biphenyl]-3-yl)adamantane (P) in dry THF (200 ml) was added to 11.4 ml (28.3 mmol) of 2.5 M hexane at -80°C. nBuLi was added dropwise over 20 min. The reaction mixture was stirred at this temperature for 1 h, then 8.50 ml (40.4 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The resulting suspension was stirred at room temperature for 1 h, then poured into 300 ml of water. The resulting mixture was extracted with dichloromethane (3×100 ml) and the combined organic extracts were washed with Na 2 SO 4 The mixture was dried at rt and then evaporated to dryness. Yield 15.8 g (99%) of a colorless glassy solid. 1 H NMR (CDCl 3 , 400 MHz): δ7.75 (d, J = 7.4 Hz, 1H), 7.42 (dt, J = 7.4, 1.4 Hz, 1H), 7.36 (d, J = 7.6 Hz, 1H), 7.32 (dt, J = 7.3, 1.3 Hz, 1H), 7.06 (d, J = 2.1 Hz, 1H), 6.83 (d, J = 2.1 Hz, 1H), 4.49 - 4.50 (m, 1H), 4.40 - 4.41 (m, 1H), 3.25 (s, 3H), 2.53 - 2.57 (m, 2H), 2.19 - 2.22 (m, 6H), 2.11 (br.s, 3H), 1.76 - 1.84 (m, 6H), 1.58 - 1.67 (m, 2H), 1.25 - 1.38 (m, 10H), 1.19 (s, 6H), 1.14 (s, 6H), 0.89 (t, J = 6.8 Hz, 3H). 13 C NMR (CDCl 3 , 100 MHz): δ151.6, 146.0, 141.8, 136.7, 136.6, 134.3, 130.3, 129.8, 129.6, 126.04, 125.99, 98.7, 83.4, 67.9, 57.2, 41.5, 37.3, 37.1, 35.7, 31.9, 31.5, 29.51, 29.46, 29.3, 29.2, 25.6, 25.0, 24.3, 22.7, 14.1.

[0093] Synthesis of 2',2'''-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(n-octyl)-[1,1'-biphenyl]-2-ol) (R) [ka] To a solution of 15.8 g (26.9 mmol) of 2-(3'-(adamantan-1-yl)-2'-(methoxymethoxy)-5'-octyl-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Q) in 1,4-dioxane (80 ml) was added successively 2.93 g (12.4 mmol) of 2,6-dibromopyridine, 26.0 g (80.7 mmol) of cesium carbonate and 30 ml of water. The resulting mixture was purged with argon for 10 min and then 1.55 g (1.34 mmol) of Pd(PPh 3 ) 4 The mixture was stirred at 100° C. for 12 hours, then cooled to room temperature and diluted with 50 ml of water. The resulting mixture was extracted with dichloromethane (3×50 ml) and the combined organic extracts were washed with Na 2 SO 4 The resulting oil was dried at 40° C. and then evaporated to dryness. 100 ml of THF, 100 ml of methanol and 5 ml of 12N HCl were added successively to the resulting oil. The reaction mixture was stirred at 60° C. overnight and then poured into 300 ml of water. The resulting mixture was extracted with dichloromethane (3×350 ml) and the combined organic extracts were washed with 5% NaHCO 3 Wash with Na 2 SO 4 The mixture was dried at 40° C. and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate=10:1, by volume). Yield 4.60 g (41%) of a mixture of two isomers as a colorless glassy solid. 1 H NMR (CDCl 3, 400 MHz): δ7.75 (s, 2H in A), 7.34 - 7.54 (m, 9H), 7.04 (s, 2H in B), 6.99 (d, J = 7.8 Hz, 2H in B), 6.98 (d, J = 7.8 Hz, 2H in A), 6.90 (d, J = 1.8 Hz, 2H in B), 6.84 (d, J = 7.8 Hz, 2H in A), 6.25 (d, J = 1.8 Hz, 2H in A), 2.46 - 2.50 (m, 4H in B), 2.18 - 2.27 (m, 4H in A), 1.78 - 1.98 (m, 16H), 1.52 - 1.71 (m, 18H), 1.11 - 1.36 (m, 20H), 0.85 - 0.91 (m, 6H). 13 C NMR (CDCl 3 , 100 MHz, signals due to minor isomers are marked with *): δ 157.94, 157.88*, 150.3, 149.7*, 139.6, 138.8*, 137.9, 137.6, 137.5*, 137.3*, 136.8*, 133.9*, 133.6, 132.3*, 131.6, 130.4, 130.2*, 129.7*, 129.3*, 128.8, 128.5, 128.2*, 127.8*, 127.7, 126.2*, 125.9, 122.3, 122.1*, 40.4, 40.2*, 37.0, 36.9*, 36.7, 36.6*, 35.4*, 35.2, 31.9, 31.6*, 29.51, 29.49*, 29.29*, 29.28, 29.12, 29.02*, 22.7, 14.1.

[0094] Synthesis of dimethylzirconium [2',2''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-olate] (complex 11) [ka] To a suspension of 551 mg (2.37 mmol) of zirconium tetrachloride in dry toluene (300 ml) at 30° C. was added 3.73 ml (10.7 mmol) of 2.9 M MeMgBr in diethyl ether in one portion via syringe. To the resulting suspension was immediately added 2.50 g (3.03 mmol) of 2',2'''-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(n-octyl)-[1,1'-biphenyl]-2-ol) (R) in one portion. The reaction mixture was stirred at room temperature for 3 hours and then evaporated to near dryness. The resulting solid was extracted with toluene (2×100 ml) and the combined organic extracts were filtered through a thin pad of Celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 10 ml of n-hexane and the resulting precipitate was filtered off (G3), washed twice with 10 ml of n-hexane and then dried in vacuum. Yield 2.22 g (91%) of a beige solid. Elemental analysis: C 67 H 85 ZrNO 2 Calculated values: C, 78.31; H, 8.34; N, 1.36. Found values: C 78.51; H, 8.60; N 1.27. 1 H NMR (C 6 D 6 , 400 MHz): δ 7.30 (d, J = 2.1 Hz, 2H), 7.23 (dd, J = 6.1, 2.1, Hz, 2H), 7.08 - 7.15 (m, 4H), 7.02 (dd, J = 6.1, 2.1 Hz, 2H), 6.85 (d, J = 2.1 Hz, 2H), 6.55 (dd, J = 8.4, 7.1 Hz, 1H), 6.44 (d, J = 8.1 Hz, 2H), 2.61 (t, J = 7.6 Hz, 4H), 2.49 - 2.58 (m, 6H), 2.33 - 2.44 (m, 6H), 2.18 (br.s, 6H), 1.95 - 2.03 (m, 6H), 1.79 - 1.88 (m, 6H), 1.68 (quintet, J = 7.6 Hz, 4H), 1.22 - 1.38 (m, 20H), 0.90 (t, J = 7.1 Hz, 6H), 0.11 (s, 6H).13 C NMR (C 6 D 6 , 100 MHz): δ 159.5, 158.3, 143.6, 139.5, 138.6, 133.7, 133.2, 132.5, 131.5, 131.2, 128.0, 127.8, 124.5, 42.9, 42.0, 38.3, 37.9, 36.5, 32.7, 32.65, 30.3, 30.1, 30.0, 23.5, 14.7.

[0095] Synthesis of dichlorozirconium [2',2''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-olate] (complex 12) [ka] To a stirred solution of dimethylzirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-olate)] (complex 11) (0.246 g, 0.239 mmol) in toluene (15 mL) was added a solution of ethylaluminum dichloride (0.52 mL, 1.01 M in hexanes, 0.53 mmol, 2.2 equiv). The reaction was stirred and heated to 60° C. for 3 h. Upon cooling, the reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in hexanes (10 mL) and filtered on a plastic fritted funnel. The filtered solid was further washed with hexanes (5 mL). The solid was collected and concentrated under high vacuum to give the product as a light grey solid (0.223 g, 87% yield). 1 H NMR (400 MHz, C 6 D 6): δ 7.30-7.18 (m, 8H), 7.13-7.07 (m, 2H), 6.88-6.79 (m, 2H), 6.54-6.47 (m, 1H), 6.46-6.32 (m, 2H), 2.61-2.53 (m, 4H), 2.48-2.36 (m, 6H), 2.36-2.24 (m, 6H), 2.24-2.03 (m, 12H), 1.87-1.74 (m, 6H), 1.72-1.58 (m, 4H), 1.47-1.07 (m, 20H), 0.95-0.84 (m, 6H).

[0096] Synthesis of (2-methylbut-2-ene-1,4-diyl)zirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-olate] (complex 13) [ka] To a stirred suspension of activated magnesium powder (0.015 g, 0.62 mmol, 6.7 equiv.) in diethyl ether (3 mL) was added a solution of dichlorozirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-olate)] (complex 12) (0.098 g, 0.092 mmol) in tetrahydrofuran (3 mL). Isoprene (0.07 mL, 0.7 mmol, 7.6 equiv.) was then added. The reaction was stirred at room temperature for 2 h. The reaction was concentrated under a stream of nitrogen and then high vacuum. The residue was stirred in hexane (15 mL) and then filtered over Celite. The filtrate was concentrated under a stream of nitrogen and then high vacuum to give the product as an orange foam (0.058 g, 59% yield). 1 H NMR (400 MHz, C 6 D 6): δ 7.38 (dd, 1H, J = 7.3, 1.5 Hz), 7.26 (td, 1H, J = 7.4, 1.5 Hz), 7.23-7.08 (m, 8H), 6.85 (d, 1H, J = 2.3 Hz), 6.80 (d, 1H, J = 2.2 Hz), 6.68-6.64 (m, 2H), 6.62-6.58 (m, 1H), 5.51 (t, 1H, J = 11.5 Hz), 2.94 (t, 1H, J = 10.5 Hz), 2.66-2.50 (m, 4H), 2.27-2.03 (m, 15H), 2.03-1.93 (m, 3H), 1.91-1.72 (m, 15H), 1.72-1.56 (m, 5H), 1.40-1.16 (m, 20H), 1.12-1.07 (m, 1H), 1.02 (t, 1H, J = 11.3 Hz), 0.92-0.86 (m, 6H).

[0097] 2-(2-(1-adamantanyl)-4-tert-butylphenoxy)tetrahydro-2H-pyran(S) [ka] To a solution of 2-(1-adamantanyl)-4-(tert-butyl)phenol (38.0 g, 133 mmol) and 3,4-dihydro-2H-pyran (22.5 g, 267 mmol) in dichloromethane (300 mL) was added p-toluenesulfonic acid monohydrate (203 mg, 1.07 mmol) at -10°C. The reaction mixture was slowly warmed to ambient temperature and stirred while monitoring the reaction by thin layer chromatography (TLC). Upon complete conversion of the starting material (as indicated by TLC, approximately 5 min at ambient temperature), sodium tert-butoxide (128 mg, 1.33 mmol) was added immediately. The resulting mixture was filtered through a plug of silica gel, which was then washed with a 1:1 dichloromethane:hexane solution. The combined filtrate was concentrated to give the product as a white solid (46.30 g, 94%). 1 H NMR (400 MHz, CDCl 3) δ 7.26 (s, 1H), 7.17 - 7.08 (m, 2H), 5.46 (s, 1H), 3.92 (t, J = 10.8 Hz, 1H), 3.65 (d, J = 11.8 Hz, 1H), 2.28 - 2.00 (m, 10H), 1.99 - 1.84 (m, 2H), 1.84 - 1.56 (m, 9H), 1.30 (s, 9H).

[0098] (3-(1-adamantanyl)-5-(tert-butyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)lithium ether complex (T) [ka] To a solution of 2-(2-(1-adamantanyl)-4-tert-butylphenoxy)tetrahydro-2H-pyran (S) (46.3 g, 126 mmol) in diethyl ether (100 mL) at ambient temperature was added n-butyllithium in hexanes (1.6 M, 82.4 mL, 132 mmol). The solution was stirred for 1 h and then concentrated to dryness. The crude product was slurried in pentane (30 mL) and stirred for 30 min. The product was isolated by filtration as a white solid (40.0 g, 71%). 1 H NMR (400 MHz, THF-d 8 ) δ 7.73 (s, 1H), 6.86 (s, 1H), 6.59 (br, 1H), 3.91 (t, J = 11.7 Hz, 1H), 3.55 - 3.43 (m, 1H), 2.27 (q, J = 12.4 Hz, 7H), 2.04 (d, J = 18.1 Hz, 5H), 1.80 (td, J = 23.8, 13.1 Hz, 9H), 1.32 (s, 9H).

[0099] 2-((3-(1-adamantanyl)-2'-bromo-5-(tert-butyl)-[1,1'-biphenyl]-2-yl)oxy)tetrahydro-2H-pyran (U) [ka] (3-(1-adamantanyl(an))-5-(tert-butyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)lithium etherate (T) (20.1 g, 44.8 mmol) was dissolved in THF (100 mL) and hexane (100 mL). 2-Bromochlorobenzene (9.44 g, 49.4 mmol) in hexane (50 mL) was added dropwise to the resulting solution at 60 °C. The reaction was stirred at 60 °C for 1 h. After the reaction was cooled to room temperature, water (100 mL) was added and the resulting mixture was stirred for 10 min. The two phases were separated and the aqueous phase was extracted with diethyl ether. The combined organic extracts were diluted with MgSO 4 The mixture was dried at rt and then concentrated under vacuum. The product was then precipitated from a minimum of pentane as a white solid, which was collected by filtration. Additional product remaining in the filtrate was purified by flash chromatography on silica gel (30% dichloromethane in hexanes). The combined yield was 87% (20.5 g). 1 H NMR (400 MHz, chloroform-d) δ 7.68 (dd, J = 30.1, 8.0 Hz, 1H), 7.53 - 7.13 (m, 4H), 7.01 (dd, J = 59.7, 2.3 Hz, 1H), 4.31 (dd, J = 8.1, 2.3 Hz, 1H), 3.79 (dd, J = 39.7, 12.0 Hz, 1H), 2.99 (dt, J = 97.6, 11.2 Hz, 1H), 2.26 (dt, J = 22.7, 12.8 Hz, 6H), 2.11 (s, 3H), 1.86 - 1.50 (m, 8H), 1.47-1.23 (m, 12H), 1.20 - 1.01 (m, 1H).

[0100] 4-(1-Adamantanyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinine (V) [ka] To a solution of 2-((3-(1-adamantanyl)-2'-bromo-5-(tert-butyl)-[1,1'-biphenyl]-2-yl)oxy)tetrahydro-2H-pyran (U) (23.5 g, 44.9 mmol) in THF (200 mL) at -78°C, n-butyllithium in hexane (1.6 M, 33.4 mL, 53.5 mmol) was added dropwise over 20 minutes. The reaction mixture was stirred at -78°C for 1 hour, and then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11.8 g, 63.1 mmol) was added. The resulting suspension was stirred at ambient temperature for 1 hour, and then poured into 100 mL of water. The resulting mixture was extracted with hexane (100 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×50 mL). The combined organic extracts were washed with MgSO 4 The mixture was dried at 37° C. and then evaporated to dryness. To the resulting residue was added isopropanol (150 mL) and the resulting solution was refluxed for 16 h. After cooling to ambient temperature, the reaction was concentrated and cooled to −20° C. for 1 h to afford the product as a white solid (16.6 g, 80%) which was isolated by filtration. 1 H NMR (400 MHz, CDCl 3 ) δ 8.17 (d, J = 8.2 Hz, 1H), 8.09 - 8.02 (m, 2H), 7.65 (t, J = 8.0 Hz, 1H), 7.45 - 7.40 (m, 2H), 5.24 (p, J = 6.1 Hz, 1H), 2.30 (br, 6H), 2.16 (br, 3H), 1.84 (br, 6H), 1.43-1.39 (m, 15H).

[0101] 2,6-Dibromo-4-ethylpyridine (W) [ka] A solution of 2,6-dibromo-4-methylpyridine (3.00 g, 12.0 mmol) in THF (5 mL) and freshly prepared LDA (1.28 g, 12.0 mmol) in THF (3 mL) were separately cooled in a cooling bath below −55° C. for 10 min. The cooled LDA solution was then slowly added to the solution of 2,6-dibromo-4-methylpyridine, which was stirred at −55° C. for 1 h. Iodomethane (1.70 g, 12.0 mmol) was then added to the reaction mixture, which was stirred at ambient temperature for 2 h. The reaction was then quenched with water and diluted with hexane. After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were diluted with MgSO 4 The mixture was dried at 40° C. and then concentrated to dryness. Purification by flash chromatography on silica gel (30% dichloromethane in hexanes) afforded the product in 67% yield (2.11 g). 1 H NMR (400 MHz, CDCl 3 ) δ 7.29 (s, 1H), 2.61 (q, J = 7.6 Hz, 2H), 1.24 (td, J = 7.7, 1.2 Hz, 3H.

[0102] 2',2'''-(4-ethylpyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) (X) [ka] To a solution of 4-(1-adamantanyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinine (V) (2.10 g, 4.91 mmol) in 1,4-dioxane (12 mL) was added 2,6-bromo-4-ethylpyridine (W) (0.65 g, 2.45 mmol), potassium carbonate (2.03 g, 14.7 mmol), Buchwald RuPhos palladacycle generation I precatalyst (Strem, CAS1028206-60-1, 27.0 mg, 0.04 mmol) and water (6 mL). The mixture was stirred at 100° C. for 16 hours, then cooled to ambient temperature and diluted with water (30 mL). The resulting mixture was diluted with hexane (20 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×50 mL). The combined organic extracts were washed with MgSO 4 The mixture was dried at 40° C. and then concentrated to dryness. The product was purified by flash chromatography on silica gel (eluting impurities with 15% dichloromethane in hexanes, then eluting product with 25% dichloromethane+2% acetone in hexanes). The product was isolated as a mixture of two isomers (1.59 g, 79%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.29 (s, 2H in A), 7.54 - 7.32 (m, 8H), 7.07 - 7.01 (m, 2H), 6.88 (s, 2H in B), 6.77 (s, 2H in B), 6.72 (s, 2H in A), 6.63 (s, 2H in B), 6.50 (s, 2H in A), 2.33 (q, J = 7.5 Hz, 2H), 2.06 - 1.77 (m, 18H), 1.62 (br, 12H), 1.13 (s, 18H in B), 0.95 (s, 18H in A), 0.88 - 0.79 (m, 3H).

[0103] Synthesis of methylzirconium [2',2''-(4-ethylpyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate] (complex 15) [ka] To a pre-cooled stirred suspension of zirconium chloride (0.142 g, 0.609 mmol, 1 equiv.) in toluene (2 mL) was added methylmaganesium bromide (0.82 mL, 3.0 M in diethyl ether, 2.5 mmol, 4.0 equiv.). A pre-cooled solution of 2',2'''-(4-ethylpyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) (X) (0.502 g, 0.609 mmol) in toluene (3 mL) was then added dropwise. The reaction was stirred at room temperature for 3 h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in hexane (20 mL) and heated to reflux. The mixture was filtered over Celite while still warm. The filtered solid was further extracted with refluxing hexanes (2 x 20 mL). The combined hexane filtrates were concentrated under a stream of nitrogen and then under high vacuum to give the product (0.424 g, 66% yield) containing hexanes (0.18 equiv.) and toluene (0.96 equiv.) as a tan-gray solid. 1 H NMR (C 6 D 6 , 400 MHz): δ 7.54 (d, 2H, J = 2.6 Hz), 7.24-7.20 (m, 2H), 7.14-7.00 (m, 8H), 6.39 (s, 2H), 2.65-2.54 (m, 6H), 2.49-2.40 (m, 6H), 2.24-2.15 (m, 6H), 2.06-1.96 (m, 6H), 1.89-1.80 (m, 6H), 1.68 (q, 2H, J = 7.6 Hz), 1.33 (s, 18H), 0.48 (t, 3H, J = 7.6 Hz), 0.14 (s, 6H).

[0104] Synthesis of dichlorozirconium [2',2''-(4-ethylpyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate] (complex 16) [ka] To a stirred solution of dimethylzirconium [2',2'''-(4-ethylpyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)] (complex 15) (0.180 g, 0.191 mmol) in toluene (5 mL) was added ethylaluminum dichloride (0.42 mL, 1.01 M in hexanes, 0.42 mmol, 2.2 equiv). The reaction was stirred and heated to 60° C. for 2 h. The reaction was concentrated under a stream of nitrogen with cooling. The residue was stirred in pentane (10 mL) and filtered. The filtered solid was further washed with additional pentane (5 mL). The filtered solid was collected and concentrated under high vacuum to give the product as a grey solid (0.147 g, 78% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ 7.51 (d, 2H, J = 2.6 Hz), 7.27-7.17 (m, 7H), 7.15-6.99 (m, 3H), 6.39 (s, 2H), 2.51-2.42 (m, 6H), 2.38-2.29 (m, 6H), 2.23-2.15 (m, 6H), 2.13-2.05 (m, 6H), 1.88-1.78 (m, 6H), 1.64 (q, 2H, J = 7.5 Hz), 1.29 (s, 18H), 0.44 (t, 3H, J = 7.5 Hz).

[0105] Synthesis of (2-methylbut-2-ene-1,4-diyl)zirconium [2',2'''-(4-ethylpyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate] (complex 17) [ka] To a stirred suspension of activated magnesium powder (0.018 g, 0.74 mmol, 5 equiv.) in diethyl ether (7 mL) was added a solution of dichlorozirconium [2',2'''-(4-ethylpyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)] (complex 16) (0.147 g, 0.149 mmol) in tetrahydrofuran (3 mL). Isoprene (0.10 mL, 1.0 mmol, 6.7 equiv.) was then added. The reaction was stirred at room temperature for 2 hours. Additional isoprene (0.10 mL, 1.0 mmol, 6.7 equiv.) was then added. The reaction was stirred at room temperature for an additional 2 hours. Additional isoprene (0.10 mL, 1.0 mmol, 6.7 equiv.) was then added. The reaction was stirred at room temperature for 3 days. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in hexanes (15 mL) and then filtered over Celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give the product as an orange solid (0.027 g, 18% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ 7.46 (d, 2H, J = 7.6 Hz), 7.40 (s, 1H), 7.30 (s, 1H), 7.31-7.25 (m, 2H), 7.25-7.20 (m, 4H), 7.07-7.00 (m, 2H), 6.61 (s, 1H), 6.53 (s, 1H), 5.57-5.47 (m, 1H), 2.96 (t, 1H, J = 10.4 Hz), 2.63 (d, 1H, J = 8.6 Hz), 2.30-2.22 (m, 3H), 2.22-2.16 (m, 3H), 2.16-2.09 (m, 9H), 2.05-1.98 (m, 3H), 1.91-1.76 (m, 17H), 1.32 (s, 9H), 1.26 (s, 9H), 1.06 (d, 1H, J = 12.2 Hz), 0.88 (t, 1H, J = 6.5 Hz), 0.56 (t, 3H, J = 7.5Hz).

[0106] Synthesis of (2-(4-methylpent-3-enyl)-but-2-ene-1,4-diyl)zirconium [2',2''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate] (complex 18) [ka] To a stirred suspension of activated magnesium powder (7 mg, 0.29 mmol, 2.5 equiv.) in diethyl ether (3 mL) was added a solution of dichlorozirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)] (complex 1) (0.111 g, 0.116 mmol) in tetrahydrofuran (10 mL). Myrcene (0.02 mL, 0.12 mmol, 1 equiv.) was then added, at which point the reaction turned a bright yellow-orange color. The reaction was stirred at room temperature for 4 days. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with hexane and then filtered over Celite. The filtrate was placed in the freezer for 1 week, after which time a solid had precipitated. The mixture was filtered over Celite and the filtrate was collected and concentrated under a stream of nitrogen and then under high vacuum to give the product as a brown glassy solid (0.087 g, 73% yield). 1 H NMR (400 MHz, C 6 D 6): δ 7.42 (d, 1H, J = 2.7 Hz), 7.39-7.32 (m, 2H), 7.29-7.21 (m, 3H), 7.19-7.16 (m, 1H), 7.13-7.06 (m, 3H), 7.05 (d, 1H, J = 2.6 Hz), 7.01 (d, 1H, J = 2.5 Hz), 6.63-6.50 (m, 3H), 5.59 (t, 1H, J = 11.6 Hz), 5.41-5.34 (m, 1H), 2.94 (t, 1H, J = 10.6 Hz), 2.71 (d, 1H, J = 9.1 Hz), 2.48-2.37 (m, 2H), 2.29-2.22 (m, 3H), 2.22-2.16 (m, 3H), 2.15-2.08 (m, 9H), 2.04-1.96 (m, 3H), 1.95-1.74 (m, 14H), 1.61 (d, 3H, J = 1.4 Hz), 1.53 (d, 3H, J = 1.2 Hz), 1.33 (s, 9H), 1.26 (s, 9H), 1.10-0.98 (m, 2H).

[0107] 4-Synthesis of シクロヘキシルチオベンズアルデヒド(Y)

change

[0108] Synthesis of 4-cyclohexylthiobenzyl alcohol (Z) [ka] To a stirred solution of 4-cyclohexylthiobenzaldehyde (Y) (6.20 g, 26.3 mmol) in ethanol (75 mL) cooled in an ice bath was added sodium borohydride (1.10 g, 29.0 mmol, 1.10 equiv) in portions. The reaction was stirred at room temperature for 5 h. The reaction was poured into a mixture of pentane (100 mL) and hydrochloric acid (100 mL, 4 M, aqueous). The mixture was poured into a separatory funnel. The organic layer was collected and the aqueous phase was further extracted with additional pentane (2×50 mL). The combined pentane extracts were washed with brine (100 mL), dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated in vacuo to give a pale yellow oil. The oil was purified by silica gel column chromatography to give the product as a clear, colorless oil (3.94 g, 67% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ 7.41 (d, 2H, J = 8.2 Hz), 7.05 (d, 2H, J = 8.5 Hz), 4.24 (d, 2H, J = 5.5 Hz), 2.98 (tt, 1H, J = 10.6, 3.7 Hz), 2.00-1.89 (m, 2H), 1.63-1.52 (m, 2H), 1.44-1.29 (m, 3H), 1.15-0.98 (m, 3H).

[0109] Synthesis of 4-cyclohexylthiobenzyl bromide (AA) [ka] To a stirred solution of 4-cyclohexylthiobenzyl alcohol (Z) (3.94 g, 17.7 mmol) in diethyl ether cooled in an ice-water bath was added phosphorus tribromide (1.9 mL, 20 mmol, 1.1 equiv). The reaction was stirred and allowed to warm to room temperature for 4 h. The reaction was then poured into cold water (200 mL). Pentane (100 mL) was then added to the water and the mixture was poured into a separatory funnel. The organic layer was collected and the aqueous phase was further extracted with additional pentane (100 mL). The combined pentane extracts were washed with water (100 mL), dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated in vacuo to give the product (3.73 g, 73% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ 7.19 (d, 2H, J = 8.3 Hz), 6.91 (d, 2H, J = 8.3 Hz), 3.96 (s, 2H), 2.95 (tt, 1H, J = 10.6, 3.7 Hz), 1.95-1.79 (m, 2H), 1.63-1.46 (m, 2H), 1.43-1.22 (m, 3H), 1.15-0.96 (m, 3H).

[0110] Synthesis of bis(trifluoromethanesulfonate)zirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate] (complex 19) [ka] To a stirred suspension of dichlorozirconium [2',2'''-(pyridin-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate] (complex 1) (0.572 g, 0.598 mmol) in toluene (5 mL) heated to 110 °C was added a solution of silver(I) trifluoromethanesulfonate (0.394 g, 1.53 mmol, 2.56 equiv) in toluene (10 mL). The reaction was stirred and heated to 110 °C for 2 h. The reaction was filtered over Celite and the filtered solid was further extracted with diethyl ether. The combined filtrate was concentrated under a stream of nitrogen and then high vacuum to give the product containing toluene (2 equiv) as an off-white solid (0.743 g, 90% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ 7.56-7.49 (m, 4H), 7.43 (d, 2H, J = 7.7 Hz), 7.32 (td, 2H, J = 7.6, 1.3 Hz), 7.14-6.99 (m, 4H), 6.41-6.36 (m, 1H), 6.33-6.29 (m, 2H), 2.30-2.22 (m, 12H), 2.21-2.13 (m, 6H), 2.02-1.93 (m, 6H), 1.90-1.81 (m, 6H), 1.21 (s, 18H).

[0111] Synthesis of bis(4-cyclohexylthiobenzyl)zirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate] (complex 20) [ka] To a stirred suspension of activated magnesium powder (0.086 g, 3.5 mmol, 2.1 equiv.) in diethyl ether (15 mL) was added dropwise a solution of 4-cyclohexylthiobenzyl bromide (AA) (0.491 g, 1.72 mmol) in diethyl ether (5 mL). The reaction was stirred at room temperature for 4 h. The reaction was filtered over Celite in a plug of glass wool and the filtrate was titrated with iodine revealing a concentration of 79.6 mM. Next, to a stirred solution of bis(trifluoromethanesulfonate)zirconium[2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)] (complex 19) (0.200 g, 0.169 mmol) in toluene (10 mL) was added the prepared solution of 4-cyclohexylthiobenzylmagnesium bromide (4.3 mL, 79.6 mM, 0.342 mmol, 2 equiv). The reaction was stirred and heated to 70° C. for 20 h. Additional 4-cyclohexylthiobenzylmagnesium bromide (2.0 mL, 79.6 mM, 0.16 mmol, 0.94 equiv) was then added. The reaction was stirred and heated at 70° C. for 2 h. The reaction was then heated to reflux for an additional 4 h. The reaction was filtered over Celite and the reaction was further extracted with additional toluene (2 mL). The combined toluene filtrates were concentrated under a stream of nitrogen and then under high vacuum. The residue was mixed with hexanes (15 mL) and heated to a gentle reflux. The mixture was removed from the heat and the supernatant removed while still warm. The residual solid was concentrated under high vacuum to give the product as an off-white solid (0.135 g, 61% yield). 1 H NMR (400 MHz, C 6 D 6): δ 7.61 (d, 2H, J = 2.6 Hz), 7.42 (dd, 2H, J = 7.5, 1.5 Hz), 7.33 (d, 4H, J = 8.2 Hz), 7.11 (d, 2H, J = 2.5 Hz), 7.04-6.92 (m, 6H), 6.78 (d, 4H, J = 8.1 Hz), 6.51-6.44 (m, 1H), 6.37-6.31 (m, 2H), 2.90 (tt, 2H, J = 10.7, 3.7 Hz), 2.54-2.44 (m, 6H), 2.41 (d, 2H, J = 11.1 Hz), 2.39-2.31 (m, 6H), 2.24-2.14 (m, 6H), 2.06-1.92 (m, 10H), 1.88-1.78 (m, 6H), 1.67-1.56 (m, 4H), 1.45-1.18 (m, 24H), 1.18-0.99 (m, 6H), 0.12 (d, 2H, J = 10.9 Hz).

[0112] Solubility of the complex General procedure: A measured amount of the complex was added to a tared vial followed by a stir bar. Dry isohexane was added in small portions and the resulting mixture was stirred after each portion of isohexane. If a clear solution formed, the solubility was reported as the range between the lower solubility boundary calculated using the total amount of solvent added to achieve a homogeneous solution and the upper solubility boundary calculated using the total amount of solvent measured before achieving a homogeneous solution. If the mixture was still inhomogeneous (visible solids or turbidity), the upper solubility boundary was taken and calculated using the total amount of solvent added. Deviations from this procedure, when used, are reported below. Toluene content is equal to the toluene associated with the molecules of the complex.

[0113] The formula used to calculate solubility is listed below. Co-crystallized solvents present in the complex are included in the mass and formula weight of the complex. The density of isohexane used in the calculations was 0.672 g / ml. Solubility data for complex 14 was taken from co-pending U.S. Patent Application No. 63 / 338169. Complex 14 was co-crystallized with 1.4 equivalents of methylcyclohexane.

[0114] Solubility (mM)=[10 6 ] * [(number of complexes in grams) / (formula mass of complex (g / mol))] / [(total volume of solvent (mL))]. Solubility (mass%) =

[0100] * [(grams of complex) / [(grams of complex)+(total volume of solvent (mL))] * (density of solvent (g / mL))].

[0115] [Table 1]

[0116] Complex 2. To a tared vial was added (2-butene-1,4-diyl)zirconium[2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)] (Complex 2) (0.0304 g, containing 0.64 equivalents of hexane, 30.6 μmol). A stir bar and dry isohexane (10.0 mL) were added. The vial was sealed and the mixture was stirred at room temperature for 30 minutes. The contents of the vial were then heated to 40° C. and the contents were stirred at this temperature for 30 minutes. The contents of the vial were then heated to 50° C. The contents of the vial were completely dissolved. The contents of the vial were then cooled to room temperature and stirred overnight. The contents of the vial remained in solution until the following morning.

[0117] Complex 3. To a tared vial was added (2-methyl-2-butene-1,4-diyl)zirconium[2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)] (Complex 3) (0.0152 g, 15.9 μmol). A stir bar and dry isohexane (5.0 mL) were added. The vial was sealed and the mixture was stirred at room temperature overnight. The contents of the vial were then heated to 30° C. for 20 minutes. The contents of the vial were then heated in 5° C. increments for 20 minutes until all of the solids had dissolved. All of the solids had dissolved at 50° C. The solution was cooled to room temperature and stirred overnight. The contents of the vial remained in solution until the following morning.

[0118] Complex 5. Dimethylzirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-olate)] (complex 5) (0.0167 g, 17.4 μmol, containing 0.2 equivalents of toluene) was added to a tared vial. A stir bar and dry isohexane (5.0 mL) were added. The vial was sealed and the mixture was stirred at room temperature. Isohexane was added to the mixture in small portions. The complex was not completely dissolved upon addition of 8.0 mL of isohexane, but the complex dissolved with stirring after a total of 10.0 mL of isohexane was added. Complex 5a. Separately, a portion of complex 5 was extracted with n-hexane (15.0 mL) and filtered over Celite. The filtrate was concentrated in vacuo to give a fraction of complex 5 free of toluene but containing n-hexane (0.61 equiv). This sample (0.0148 g, 14.9 μmol) was added to a tared vial and isohexane was added in 0.5 mL increments with stirring until a total of 2.0 mL of isohexane had been added. The suspension was stirred for 2 hours. Isohexane was then added in 0.5 mL increments up to 5.0 mL. Isohexane was then added in 0.5 mL increments up to 8.0 mL. The resulting suspension was then heated to 30° C., at which point the complex had completely dissolved. The mixture was then cooled to room temperature, at which point a solid precipitated.

[0119] Complex 7. To a tared vial was added (2-methylbut-2-ene-1,4-diyl)zirconium [2',2''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-olate)] (0.0160 g, 15.7 μmol). Isohexane was added in 0.5 mL portions to a total of 1.0 mL. The resulting suspension was stirred for 3.5 hours. Isohexane was then added in small portions up to a total of 5.0 mL and the resulting suspension was stirred overnight. Isohexane was added in 0.5 mL portions to 6.0 mL and the suspension was stirred for 50 minutes. Isohexane was added to a total of 6.5 mL and the suspension was stirred for 25 minutes. Isohexane was added to a total of 7.0 mL and the suspension was stirred for 15 minutes. Isohexane was added up to a total of 7.5 mL, at which point all solids had dissolved.

[0120] Complex 8. Dimethylzirconium [2',2''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-olate)] (complex 8) was mixed with hexane. The mixture was filtered through celite and glass wool. The filtrate was left at room temperature overnight to induce precipitation. The resulting mixture was then filtered again through celite and glass wool. The filtrate was cooled to -35°C for 3 days, at which time white clusters precipitated. The clusters were isolated and concentrated under high vacuum for 5 hours to remove any residual toluene. The resulting solid was weighed into a tared vial (0.0129 g, 0.52 equiv., hexane, 12.0 μmol). A stir bar was added to the vial. With stirring, isohexane was added in 0.5 mL increments (with 15 minutes of stirring between additions) until 2.5 mL was reached, at which point much of the material had dissolved. The mixture was stirred overnight. By the next morning, the mixture was white and cloudy. Therefore, additional isohexane was added in 0.5 mL increments until a total of 4.0 mL was reached, at which point the mixture remained cloudy white. The sealed vial was heated to 70° C., at which point the mixture remained cloudy white.

[0121] Complex 10. To a tared vial was added (2-methylbut-2-ene-1,4-diyl)zirconium[2',2''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-olate)] (Complex 10) (0.0160 g, containing 0.4 equivalents of toluene, 15.0 μmol) and a stir bar. With stirring, isohexane was added in 0.5 mL increments until 5.0 mL was reached (stirring at least 15 minutes between additions). The mixture, which was a cloudy tan-brown suspension, was then heated to 30° C. The mixture was then heated in additional 5° C. increments (the mixture was stirred for at least 15 minutes between each temperature change) until the mixture reached 50° C., at which point the mixture remained a cloudy tan-brown suspension.

[0122] Complex 11. Dimethylzirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-olate)] (0.0156 g, 15.2 μmol, containing 0.1 equivalent of toluene) was added to a tared vial. Isohexane was then added with stirring to 5.0 mL. Isohexane was added in small increments to 14.0 mL, at which point the mixture remained a suspension. Complex 13. To a tared vial was added (2-methyl-2-butene-1,4-diyl)zirconium[2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-olate)] (complex 13) (0.0147 g, 13.8 μmol). Dry isohexane (0.1 mL) was then added. Additional dry isohexane (0.1 mL) was then added. The complex was completely dissolved.

[0123] Polymerization Example Toluene (ExxonMobil Chemical - anhydrous, N 2Pre-catalyst solutions were made using hexane (stored under reduced pressure) (98%) or isohexane (ExxonMobil Chemical - polymerization grade and purified as described below). Pre-catalyst solutions were typically 0.25 mmol / L. The solvent, polymerization grade toluene and / or isohexane, was supplied by ExxonMobil Chemical Co. and was purified by passage through a series of columns: two 500 cc Oxyclear cylinders in series manufactured by Labclear (Oakland, Calif), followed by two 500 cc columns in series packed with dry 3 Å molecular sieves (8-12 mesh; Aldrich Chemical Company), and two 500 cc columns in series packed with dry 5 Å molecular sieves (8-12 mesh; Aldrich Chemical Company).

[0124] Polymerization grade propylene (C 3 The polymerization grade propylene was further purified using a series of columns: a 2250 cc Oxiclear cylinder from Labclear, then a 2250 cc column packed with 3 Å molecular sieves (8-12 mesh; Aldrich Chemical Company), then two 500 cc columns in series packed with 5 Å molecular sieves (8-12 mesh; Aldrich Chemical Company), then a 500 cc column packed with Selexsorb CD (BASF), and finally a 500 cc column packed with Selexsorb COS (BASF). Activation of the precatalyst was with either dimethylanilinium tetrakisperfluorophenylborate (Boulder Scientific or Albemarle Corp; Act ID=A) or (hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate (Boulder Scientific; Act ID=B) supplied as a 10 wt % solution in methylcyclohexane. Activators were typically used as 0.25 mmol / L solutions in toluene or isohexane. Tri-n-octylaluminum (TnOAl or TNOA, neat, AkzoNobel) was also used as an activator and scavenger prior to introducing the precatalyst into the reactor. TNOA was typically used as a 5 mmol / L solution in toluene or isohexane.

[0125] Reactor description and preparation: Polymerizations were performed in an inert atmosphere (N) using an autoclave equipped with an external heater for temperature control, a glass insert (internal reactor volume 22.5 mL), septum inlets to regulate the nitrogen and propylene feed rates, and a disposable PEEK mechanical stirrer (800 RPM). 2 The autoclave was prepared by purging with dry nitrogen at 110° C. or 115° C. for 5 hours and then at 25° C. for 5 hours.

[0126] Propylene Polymerization (PP): The reactor was prepared as described above, then heated to 40° C., then purged with propylene gas at atmospheric pressure. Toluene or isohexane, liquid propylene (1.0 mL), and scavenger (TNOA, 0.5 μmol) were added via syringe. The reactor was then brought to process temperature (70° C. or 100° C.) with stirring at 800 RPM. The activator solution, followed by the pre-catalyst solution, was injected into the reactor at process conditions via syringe. The reactor temperature was monitored and typically maintained within + / - 1° C. The polymerization was stopped by adding approximately 50 psi compressed dry air gas mixture to the autoclave for approximately 30 seconds. The polymerization was quenched based on a pre-determined pressure drop (maximum quench value) or for a maximum of 30 minutes. The reactor was cooled and vented. The polymer was isolated after the solvent was removed in vacuum. The actual quench time is reported as quench time (s). The reported yields include the total mass of polymer and residual catalyst. Catalyst activities are reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g / mmol·hr). Examples of propylene homopolymerization are reported in Table 2, with further characterization in Table 3.

[0127] Polymer characterization For analytical testing, solutions of polymer samples were prepared by dissolving the polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity, Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%, Aldrich) in a shaker oven at 165°C for approximately 3 hours. Typical concentrations of polymer in solution were between 0.1-0.9 mg / mL, with a BHT concentration of 1.25 mg BHT per mL of TCB. Samples were cooled to 135°C for testing.

[0128] High temperature size exclusion chromatography was performed using an automated "Fast GPC" system as described in U.S. Patent Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388, each of which is incorporated herein by reference. Molecular weights (weight average molecular weight (Mw), number average molecular weight (Mn) and z-average molecular weight (Mz)) and molecular weight distributions (MWD=Mw / Mn), sometimes also referred to as the polydispersity index (PDI) of the polymers, were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD) and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene calibration kit SM-10: Mp (peak Mw) between 5000 and 3,390,000). Alternatively, samples were measured by gel permeation chromatography using a Symyx Technology GPC equipped with a dual wavelength infrared detector and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene calibration kit SM-10: Mp (peak Mw) between 580 and 3,039,000). Samples (250 μL of polymer solution in TCB was injected into the system) were run using three Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5 mm columns in series with an eluent flow rate of 2.0 mL / min (sample temperature 135° C., oven / column 165° C.). No column broadening correction was used. Numerical analysis was performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. Molecular weights obtained are relative to linear polystyrene standards. Molecular weight data are reported in Table 2 under the headings Mn, Mw, Mz and PDI as defined above.

[0129] Differential scanning calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting points of the polymers. The samples were pre-annealed at 220° C. for 15 minutes and then cooled at room temperature overnight. The samples were then heated to 220° C. at a rate of 100° C. / min and then cooled at a rate of 50° C. / min. Melting points were collected during the heating period. The results are reported under the heading Tm (° C.) in Table 2.

[0130] 13 C NMR spectroscopy was used to characterize several polypropylene polymer samples produced in the experiments collected in Table 2. This data is collected in Table 3. Unless otherwise indicated, 13 d Polymer samples for C NMR spectroscopy 2 - Dissolved in 1,1,2,2-tetrachloroethane, 150MHz 13 Samples were recorded at 125° C. using an NMR spectrometer using C NMR frequencies. Polymer resonance peaks are referenced to mmmm=21.8 ppm. Calculations involved in the characterization of polymers by NMR follow the work of F. A. Bovey in "Polymer Conformation and Configuration" Academic Press, New York 1969 and J. Randall in "Polymer Sequence Determination, Carbon-13 NMR Method", Academic Press, New York, 1977.

[0131] Steric defects, measured as "steric defects / 10,000 monomer units", are calculated from the sum of the intensities of the mmrr, mmrm+rrmr and rmrm resonance peaks multiplied by 5000. The intensities used in this calculation are normalized to the total number of monomers in the sample. Methods for measuring 2,1 regiodefects / 10,000 monomers and 1,3 regiodefects / 10,000 monomers follow standard methods. Additional references include Grassi, A. et.al. Macromolecules, 1988, v.21, pp. 617-622 and Busico et.al. Macromolecules, 1994, v.27, pp. 7538-7543. The average mesolan length = 10000 / [(steric defects / 10000C) + (2,1-position defects / 10000C) + (1,3-position defects / 10000C)]. The polymerization results are collected in Tables 2 and 3 below. "Example Number (Ex#)" represents the example number. Example numbers beginning with "C" are comparative examples. "Cat ID" identifies the pre-catalyst used in this experiment. The corresponding numbers identifying the pre-catalyst (also called pre-catalyst, catalyst, complex or compound) are in the synthetic experiment section. T (°C) is the polymerization temperature, which was typically maintained within + / - 1°C. "Yield" is the polymer yield, not corrected for catalyst residues. "Quench Time" is the actual time the polymerization was carried out in seconds. For propylene homopolymerization runs, the quench value indicates the maximum set pressure drop (conversion) of propylene (for PP runs) during the polymerization. Activity is reported in grams of polymer per mmol of catalyst per hour.

[0132] Standard polymerization conditions included 0.015 μmol catalyst complex, 1.1 equivalents of activator, 0.5 μmol TNOA scavenger, 1.0 ml propylene, 4.1 ml total solvent, with a quench value of 8 psi pressure drop or 30 minutes maximum reaction time. Activator A was N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator and activator B was (hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate. When activator A was used, both the precatalyst and activator solutions were in toluene. When activator B was used, both the precatalyst and activator solutions were in isohexane. The small amount of methylcyclohexane (MCH) came from activator B, which was supplied by the manufacturer as a 10 wt. % solution in methylcyclohexane.

[0133] [Table 2] JPEG2025515175000055.jpg244156 JPEG2025515175000056.jpg244153 JPEG2025515175000057.jpg245124 [Table 3] JPEG2025515175000059.jpg24494 Certain embodiments and features are described using a set of numerical upper limits and a set of numerical lower limits. It should be understood that ranges including any combination of two values, such as any combination of a lower value with any combination of a higher value, any combination of two lower values, and / or any combination of two higher values, are contemplated unless otherwise indicated. Certain lower limits, upper limits, and ranges can be found in one or more claims below. All numerical values ​​are "about" or "approximately" their stated values, taking into account experimental error and variation that would be expected by one of ordinary skill in the art. Any values ​​in the table can be presented with an additional + / - 10% as the endpoints of the ranges defining their respective measurements or properties. All documents cited herein, including any priority documents and / or test procedures, are incorporated herein by reference to the extent that they are not inconsistent with the present specification. As is apparent from the above general description and specific embodiments, the present disclosure has been illustrated and described in its various forms, but various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, the present disclosure is not intended to be limited thereby.

[0134] While this disclosure has been described with respect to certain embodiments and examples, those skilled in the art, having the benefit of this disclosure, will understand that other embodiments may be devised that do not depart from the scope and spirit of the present disclosure.

Claims

1. A catalyst compound represented by formula (I): 【Chemistry 1】 (I) (In the formula, M is a Group 3, 4 or 5 metal; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 Or R 7 and R 8 may be joined to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or adjacent R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 any two or more of may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 are each independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 Or R 17 and R 19 may be joined together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; L is a Lewis base; each X is independently a hydrocarbyl or substituted hydrocarbyl ligand, and at least one X is a non-aromatic hydrocarbyl ligand having 9 or more carbon atoms, or a substituted hydrocarbyl ligand having at least 5 or more carbon atoms, or when n is 2, both X's together may be hydrocarbyl or substituted hydrocarbyls containing 4 or more carbon atoms and forming a 5-membered cyclic ring structure with M; n is 1, 2 or 3; m is 0, 1 or 2; n+m is 4 or less, any two L groups may be joined together to form a bidentate Lewis base; The X group may be linked to the L group to form a monoanionic bidentate group.

2. n is 2, m is 0 or 1 (preferably 0), and each X is represented by one of formulas Ia, Ib, Ic, or Id; R 20 , R 20’ , R 21 , R 21’ , R 22 , R 22’ , R 23 , R 23’ are independently hydrogen or C 1 -C 20 2. The catalyst compound of claim 1, which is hydrocarbyl and the dashed line represents a bond to the metal atom M. 【Chemistry 2】

3. n is 2 and at least one of X is C 9 -C 40 Non-aromatic hydrocarbyl ligands, preferably C 9 -C 20 Non-aromatic hydrocarbyl ligands, or more preferably C 10 -C 20 Non-aromatic hydrocarbyl ligands, or more preferably C 12 -C 20 A non-aromatic hydrocarbyl ligand, and the other X is C 1 -C 40 Hydrocarbyl or substituted hydrocarbyl ligands, preferably C 1 -C 20 10. The catalyst compound of claim 1 which is a hydrocarbyl or substituted hydrocarbyl ligand.

4. At least one of X is C 5 -C 40 Substituted hydrocarbyl ligands, preferably C 5 -C 30 Substituted hydrocarbyl ligands, preferably C 7 -C 30 Substituted hydrocarbyl ligands, more preferably C 10 -C 30 Substituted hydrocarbyl ligands, or more preferably C 12 -C 30 10. The catalyst compound of claim 1 which is a substituted hydrocarbyl ligand.

5. The substituted hydrocarbyl ligand is SiR 30 3 , GeR 30 3 , OR 30 , S.R. 30 , N.R. 30 2 R 30 Each of them is independently C 1 -C 10 Hydrocarbyl, preferably C 1 -C 10 Alkyl, C 7 -C 10 Alkylaryl or C 7 -C 10 5. The catalyst compound of claim 4, selected from arylalkyl.

6. m is 0, n is 2, and two Xs taken together form a 5-membered cyclic ring structure with M; 4 -C 40 10. The catalyst compound of claim 1 which is a hydrocarbyl or substituted hydrocarbyl.

7. m is 0, n is 2, and each X is represented by formula Ic; R 20 , R 20’ , R 21 , R 22 , R 23 , R 23’ are each independently hydrogen or C 1 -C 20 3. The catalyst compound of claim 2 which is a hydrocarbyl.

8. m is 0, n is 2, and each X is represented by formula Ic; R 20 , R 20’ , R 23 , R 23’ are each independently hydrogen; R 21 and R 22 are each independently hydrogen or hydrocarbyl, or R 21 and R 22 One of the groups is hydrogen and the other is hydrogen or hydrocarbyl, preferably hydrogen or C 1 -C 20 Hydrocarbyl, more preferably hydrogen or C 1 -C 10 The catalyst compound of claim 2, which may be a hydrocarbyl, more preferably hydrogen, methyl or 4-methylpent-3-enyl.

9. R 4 and R 5 is adamantanyl, R 2 and R 7 But, C 4 -C 40 , preferably C 4 -C 8 , hydrocarbyl, more preferably tert-butyl hydrocarbyl, m is 0, n is 2, and each X is represented by formula Ic, preferably R 20 , R 20’ , R 23 , R 23’ is hydrogen, R 21 and R 22 are each hydrogen or hydrocarbyl, preferably R 21 and R 22 3. The catalyst compound of claim 2, wherein one of is hydrogen and the other is hydrocarbyl.

10. R 21 and R 22 One of them is hydrogen and the other is C 1 -C 20 Hydrocarbyl, preferably C 1 -C 10 The catalyst compound according to any one of claims 1 to 9, which may be hydrocarbyl.

11. below: 【Chemistry 3】 2. The catalyst compound of claim 1, wherein

12. A catalyst system comprising an activator, preferably a non-aromatic hydrocarbon, and optionally a support material, and a catalyst compound according to any of claims 1 to 11.

13. A homogeneous solution, an aliphatic hydrocarbon solvent; and at least one catalyst compound according to any one of claims 1 to 11, wherein the concentration of the at least one catalyst compound is 0.20% by weight or more (alternatively 0.25% by weight or more, alternatively 0.30% by weight or more, alternatively 0.35% by weight or more, alternatively 0.40% by weight or more, alternatively 0.50% by weight or more, alternatively 1.0% by weight or more, alternatively 2.0% by weight or more).

14. 14. The homogeneous solution of claim 13, wherein the aliphatic hydrocarbon solvent is isohexane, cyclohexane, methylcyclohexane, pentane, isopentane, heptane, an isoparaffinic solvent, a non-aromatic cyclic solvent, or a combination thereof.

15. 13. A method for producing a propylene or ethylene based polymer or copolymer, comprising the step of polymerizing propylene and / or ethylene and optional comonomers by contacting them with the catalyst system of claim 12 in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form a propylene or ethylene based polymer or copolymer.

16. 16. The process of claim 15, wherein the catalyst system and the activator are fed separately to the reactor.

17. 16. The method of claim 15, wherein the catalyst system and activator are premixed prior to being fed to the reactor.

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