Substituted pyridine-2, 6-bis (phenylene phenolate) complexes with enhanced solubility useful as olefin polymerization catalyst components

Abstract

Exemplary embodiments of the present technical progress include pyridine-2, 6-bis (phenylene phenolate) complexes that can be used as catalyst components for olefin polymerization and have improved solubility in non-aromatic hydrocarbons (e.g., isohexane). Improved solubility of these complexes is achieved by modifying the ligand backbone at specific positions, which results in improved solubility, but does not adversely affect the performance of the complexes when used as catalysts for olefin polymerization.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 338,164, filed on May 4, 2022, the disclosure of which is incorporated herein by reference. Technical Field

[0002] The present disclosure relates to bis(arylphenolate) Lewis base transition metal complexes, catalyst systems comprising the bis(arylphenolate) Lewis base transition metal complexes, and polymerization processes for producing polyolefin polymers such as polyethylene-based polymers and polypropylene-based polymers. Background Art

[0003] Polyolefins, such as polyethylene, typically have comonomers, such as hexene, incorporated into the polyethylene backbone. These copolymers provide varying physical properties compared to polyethylene itself and are typically prepared in low pressure reactors using, for example, solution, slurry or gas phase polymerization processes. Polymerization can be carried out in the presence of catalyst systems such as those using Ziegler-Natta catalysts, chromium-based catalysts or metallocene catalysts.

[0004] In addition, the procatalyst (neutral, unactivated complex) should be thermally stable at ambient and above ambient temperatures because they are typically stored for weeks before use. 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 generally difficult to maintain high catalyst activity and high molecular weight capabilities because these two properties decrease fairly consistently with increasing reactor temperature. Due to the need for a wide range of polyolefin products from high-density polyethylene (HDPE) to elastomers (e.g., thermoplastic elastomers (TPE), ethylene-propylene-diene (EPDM)), many different catalyst systems may be required because a single catalyst is unlikely to be able to meet all the needs for producing these various polyolefin products. The stringent set of requirements required to develop and produce new polyolefin products makes it a highly challenging endeavor to identify suitable catalysts for a given product and production process.

[0005] Aromatic solvents are commonly used to dissolve catalyst components in industrial olefin polymerization processes. However, replacing aromatic solvents with non-aromatic solvents such as isohexane is often challenging due to the poor solubility of catalyst components in non-aromatic solvents.

[0006] Further information on the general prior art of non-metallocene 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 hereby incorporated by reference.

[0007] For further information about the complex, see: 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, the entire contents of each of which are hereby incorporated by reference. Summary of the invention SUMMARY OF THE INVENTION

[0008] The catalyst compound represented by formula (I): in: M is a Group 3, 4 or 5 metal; L is a Lewis base; X is an anionic ligand; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 9 , R 10 , R 11 and R 12 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 9 and R 10 , R 10 and R 11 or R 11 and R 12 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 13 , R 14 , R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 13 and R 14 , R 14 and R 15 or R 15 and R 16 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 or R 17 and R 19One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; Any two L groups can be linked together to form a bidentate Lewis base; The X group can be linked to the L group to form a monoanionic bidentate group; Any two X groups can be linked together to form a dianionic ligand group; and the condition is R 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 At least one of them independently contains A(R a )(R b )(R c ) in the form of a silyl or germanyl group, wherein A is Si or Ge, and R a , R b and R c Each of C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon group, or R a and R b , R a and R c or R b and R c One or more pairs of may be linked to form one or more substituted hydrocarbyl rings or unsubstituted hydrocarbyl rings. DETAILED DESCRIPTION OF THE INVENTION

[0009] Exemplary embodiments of the present technological advances include pyridine-2,6-bis(phenylenephenolate) complexes that are useful as catalyst components for olefin polymerization and have improved solubility in non-aromatic hydrocarbons such as isohexane. The improved solubility of these complexes is achieved by modifying the ligand backbone at specific positions, which results in improved solubility, but does not adversely affect the performance of the complex when used as a catalyst for olefin polymerization.

[0010] For purposes of this disclosure, the new numbering scheme for the Periodic Table Groups is used as described in Chemical and Engineering News, v. 63(5), pg. 27, (1985). Thus, a "Group 4 metal" is an element selected from Group 4 of the Periodic Table, such as Hf, Ti, or Zr.

[0011] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Ph is phenyl, tBu is tert-butyl, MAO is methylaluminoxane, 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 pressure, equiv. is equivalent, and RPM is revolutions per minute.

[0012] The specification describes transition metal complexes. The term complex is used to describe molecules in which an auxiliary ligand is coordinated to a central transition metal atom. The ligand is so large and stably bonded to the transition metal that it maintains its influence during catalyst application (e.g., polymerization). The ligand can be coordinated to the transition metal by covalent bonds and / or electron-donating coordination or intermediate bonds. An activator is generally used to activate transition metal complexes to exert their polymerization or oligomerization functions, without wishing to be bound by theory, and the activator is believed to produce cations due to the removal of anionic groups (commonly referred to as leaving groups) from transition metals.

[0013] The terms "substituent," "radical," "group," and "moiety" are used interchangeably.

[0014] "Conversion" is the amount of monomer converted to polymer product and is reported as mol% and is calculated based on polymer yield and the amount of monomer fed to the reactor.

[0015] "Catalyst activity" is a measure of how active a catalyst is and is reported as grams of product polymer (P) produced per mmol of catalyst (cat) used per hour (gP.mmolcat -1 .h -1 ).

[0016] The term "heteroatom" refers to any Group 13-17 element excluding carbon. Heteroatoms may include B, Si, Ge, Sn, N, P, As, O, S, Se, Te, F, Cl, Br, and I. The term "heteroatom" may include the above elements with hydrogen attached, such as BH, BH2, SiH2, OH, NH, NH2, etc. The term "substituted heteroatom" describes heteroatoms in which one or more of these hydrogen atoms are replaced by a hydrocarbyl or substituted hydrocarbyl(s).

[0017] Unless otherwise indicated (e.g., the definitions of "substituted hydrocarbyl," "substituted aromatic," etc.), the term "substituted" means that at least one hydrogen atom has been replaced by at least one non-hydrogen group, such as a hydrocarbyl, 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, wherein each R* is independently a hydrocarbyl or a halocarbyl radical, and two or more R* may be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted into the hydrocarbyl ring.

[0018] The term "substituted hydrocarbyl" refers to a hydrocarbyl group wherein at least one of the hydrogen atoms of the hydrocarbyl group has been replaced by at least one heteroatom (e.g., a halogen, such as Br, Cl, F, or I) or a 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, wherein each R* is independently a hydrocarbyl or a halocarbon group, and two or more R* may be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated, substituted or unsubstituted hydrocarbyl group, or an aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted into the hydrocarbyl ring. The term "hydrocarbyl-substituted phenyl" refers to a phenyl group having 1, 2, 3, 4, or 5 hydrogen groups replaced by hydrocarbyl or substituted hydrocarbyl groups. For example, a "hydrocarbyl-substituted phenyl" group may be represented by the formula: Where R a , R b , R c , R d and R e Each of which can be independently selected from hydrogen, C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon group, heteroatom or heteroatom-containing group (provided that R a , R b , R c , R d and R e At least one of them is not H), or R a , R b , R c , R d and R eTwo or more of these can be linked together to form C4-C 62 Cyclic or polycyclic hydrocarbon ring structures, or combinations thereof.

[0019] The term "substituted aromatic" refers to aromatic groups having one or more hydrogen radicals replaced with hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing groups.

[0020] The term "substituted phenyl" refers to a phenyl group having one or more hydrogen radicals replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0021] The term "substituted carbazole" refers to a carbazole group having one or more hydrogen groups replaced with a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

[0022] The term "substituted naphthyl" refers to a naphthyl group having one or more hydrogen groups replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0023] The term "substituted anthracenyl" refers to anthracenyl groups having one or more hydrogen groups replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0024] The term "substituted fluorenyl" refers to a fluorenyl group having one or more hydrogen radicals replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0025] The terms trihydrocarbylsilyl and trihydrocarbylgermyl refer to silyl or germyl groups combined with three hydrocarbyl groups. Examples of suitable trihydrocarbylsilyl and trihydrocarbylgermyl groups may include trimethylsilyl, trimethylgermyl, triethylsilyl, triethylgermyl, and all isomers of tripropylsilyl, tripropylgermyl, tributylsilyl, tributylgermyl, tripentylsilyl, tripentylgermyl, butyldimethylsilyl, butyldimethylgermyl, dimethyloctylsilyl, dimethyloctylgermyl, and the like.

[0026] The terms dihydrocarbylamino and dihydrocarbylphosphino refer to nitrogen or phosphorus groups 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, etc.

[0027] The term "substituted adamantyl" refers to an adamantyl group having one or more hydrogen groups replaced with a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

[0028] The terms "alkoxy" and "alkoxide" refer to an alkyl or aryl group bonded to an oxygen atom, such as an alkyl ether or aryl ether group attached to an oxygen atom, and may include groups in which the alkyl / aryl group is C1-C 10 The alkyl radicals may be straight chain, branched or cyclic alkyl radicals. The alkyl radicals may be saturated or unsaturated. Examples of suitable alkoxy radicals may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy.

[0029] The term "aryl" or "aryl group" refers to aromatic rings and substituted variants thereof, for example phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O or S. As used herein, the term "aromatic" also refers to quasi-aromatic heterocycles, which are heterocyclic substituents having similar properties and structure (almost planar) to aromatic heterocyclic ligands, but which do not fall within the definition of aromatic; likewise, the term aromatic also refers to substituted aromatic compounds.

[0030] The term "aralkyl" refers to an aryl group in which a hydrogen has been replaced with an alkyl or substituted alkyl group. For example, 3,5'-di-tert-butylphenylindenyl is an indene substituted with an aralkyl group. When an aralkyl group is a substituent on another group, it is bonded to that group via the aryl group.

[0031] The term "alkaryl" refers to an alkyl group in which a hydrogen has been replaced with an aryl or substituted aryl group. For example, phenethyl indenyl is an indene substituted with an ethyl group bonded to a phenyl group. When an alkaryl group is a substituent on another group, it is bonded to that group via an alkyl group.

[0032] The term "ring atoms" refers to atoms that are part of a cyclic ring structure. According to this definition, benzyl has 6 ring carbon atoms and tetrahydrofuran has 5 ring carbon atoms.

[0033] A heterocycle is a ring having heteroatoms in the ring structure, as opposed to a heteroatom-substituted ring in which hydrogens on a ring atom are replaced by heteroatoms. For example, tetrahydrofuran is a heterocycle and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles may include pyridine, imidazole, and thiazole.

[0034] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" are used interchangeably and are defined to mean a group consisting only of hydrogen and carbon atoms. For example, a hydrocarbyl radical may be C1-C 100A group which may be linear, branched or cyclic and, when cyclic, may be aromatic or non-aromatic. Examples of such groups may 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., isopentyl, cyclopentyl), hexyl (e.g., cyclohexyl), octyl (e.g., cyclooctyl), nonyl, decyl (e.g., adamantyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or triacontyl, and aryl groups such as phenyl, benzyl and naphthyl.

[0035] The terms "adamantyl" and "adamantanyl" may be used interchangeably.

[0036] As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z average molecular weight, wt% is the weight percentage, and mol% is the mole percentage. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are g / mol.

[0037] As used herein, unless otherwise indicated, "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.

[0038] Unless otherwise indicated, all melting points (Tm) are differential scanning calorimetry (DSC) second melts.

[0039] 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," "procatalyst compound," and "procatalyst complex" are used interchangeably. When "catalyst system" is used to describe such a pairing before activation, it refers to an unactivated catalyst complex (procatalyst) together with an activator and, optionally, a co-activator. When it is used to describe such a pairing after activation, it refers to an activated complex and an activator or other charge-balancing structural part. The transition metal compound can be neutral, as in a procatalyst, or a charged species with a counterion, as in an activated catalyst system. For the purposes of this disclosure and its claims, when a catalyst system is described as comprising a neutral stable form of a component, it will be understood by those skilled in the art that the ionic form of the component is a form that reacts with a monomer to produce a polymer. A polymerization catalyst system is a catalyst system that can polymerize a monomer into a polymer. In addition, the catalyst compounds and activators represented by the structural formulas herein are intended to cover catalyst compounds and activators in neutral and ionic forms.

[0040] In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a procatalyst compound, a catalyst compound, or a transition metal compound, and these terms are used interchangeably.

[0041] "Anionic ligands" are negatively charged ligands that donate one or more electron pairs to a metal ion. "Lewis bases" are neutrally charged ligands that donate one or more electron pairs to a metal ion. Examples of Lewis bases include diethyl ether, trimethylamine, pyridine, tetrahydrofuran, dimethyl sulfide, and triphenylphosphine. The term "heterocyclic Lewis base" refers to a Lewis base that is also heterocyclic. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan. Bis(arylphenolate)Lewis base ligands are tridentate ligands that bind to a metal via two anion donors (phenolates) and one heterocyclic Lewis base donor (e.g., pyridyl). Bis(arylphenolate)heterocyclic ligands are tridentate ligands that bind to a metal via two anion donors (phenolates) and one heterocyclic Lewis base donor.

[0042] The term "continuous" refers to a system that operates without interruption or stopping. For example, a continuous process for making a polymer would be one in which the reactants are continuously introduced into one or more reactors and the polymer product is continuously withdrawn. Transition Metal Complexes

[0043] In at least one embodiment, the catalyst compound represented by formula (I) is as follows. in: M is a Group 3, 4 or 5 metal; L is a Lewis base; X is an anionic ligand; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or 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 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 9 , R 10 , R 11 and R 12 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 9 and R 10 , R 10 and R 11 or R 11 and R 12 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 13 , R 14 , R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R13 and R 14 , R 14 and R 15 or R 15 and R 16 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 or R 17 and R 19 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; Any two L groups can be linked together to form a bidentate Lewis base; The X group can be linked to the L group to form a monoanionic bidentate group; Any two X groups can be linked together to form a dianionic ligand group; and the condition is R 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 At least one of them independently contains A(R a )(R b )(R c ) in the form of a silyl or germanyl group, wherein A is Si or Ge, and R a , R b and R c Each of C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon group, or R a and R b , R a and Rc or R b and R c One or more pairs of may be linked to form one or more substituted hydrocarbyl rings or unsubstituted hydrocarbyl rings.

[0044] In at least one embodiment, the catalyst compound represented by formula (II) is as follows. in: M is a Group 3, 4 or 5 metal; L is a Lewis base; X is an anionic ligand; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; Each of A' and A" is independently Si or Ge; and R a , R b , R c , R d , R e and R f Each of C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon group, or R a and R b , R a and R c , R b and R c , R d and R e , R d and R f or R e and R f One or more pairs of may be linked to form one or more substituted hydrocarbyl rings or unsubstituted hydrocarbyl rings; R 1 , R 3 , R 4 , R 5 , R 6 and R 8 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 3 and R 4 or R 5 and R 6 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R9 , R 10 , R 11 and R 12 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 9 and R 10 , R 10 and R 11 or R 11 and R 12 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 13 , R 14 , R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 13 and R 14 , R 14 and R 15 or R 15 and R 16 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 or R 17 and R 19 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; Any two L groups can 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; and Any two X groups may be linked together to form a dianionic ligand group.

[0045] For example, M of formula (I) or (II) may be a Group 3, 4 or 5 metal, for example M may be a Group 4 metal. Group 4 metals may include zirconium, titanium and hafnium. In at least one embodiment, M is zirconium or hafnium.

[0046] Each L of formula (I) or (II) can be independently selected from ether, amine, phosphine, thioether, ester, Et2O, MeOtBu, Et3N, PhNMe2, MePh2N, tetrahydrofuran and dimethyl sulfide, and each X can be independently selected from methyl, benzyl, trimethylsilyl, methyl (trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydride (hydrido), chloro (chloro), fluoro (fluoro), bromo (bromo), iodo (iodo), trifluoromethanesulfonate, dimethylamino (dimethylamido), diethylamino (diethylamido), dipropylamino (dipropylamido) and diisopropylamino (diisopropylamido). In at least one embodiment, n of formula (I) or (II) is 2 and each X is independently chloro, benzyl or methyl.

[0047] R of formula (I) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Each of which can be independently selected from hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon, alkoxy, silyl, amino, aryloxy, halogen or phosphine, 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 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms.

[0048] R of formula (II) 1 , R 3 , R 4 , R 5 , R 6 , R8 Each of which can be independently selected from hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon, alkoxy, silyl, amino, aryloxy, halogen or phosphine, or R 3 and R 4 or R 5 and R 6 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms.

[0049] 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 or R of formula (II) 1 , R 3 , R 4 , R 5 , R 6 , R 8 One or more of the groups are independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, substituted phenyl, biphenyl or isomers thereof, which may be halogenated (e.g., perfluoropropyl, perfluorobutyl, perfluoroethyl, perfluoromethyl), substituted hydrocarbyl and all isomers of substituted hydrocarbyl, including trimethylsilylpropyl, trimethylsilylmethyl, trimethylsilylethyl, phenyl or all isomers of hydrocarbyl-substituted phenyl, including methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, dipropylphenyl, tripropylphenyl, dimethylethylphenyl, dimethylpropylphenyl, dimethylbutylphenyl or dipropylmethylphenyl.

[0050] For example, R of formula (I) or (II) 4 and R 5 Can be independently C1-C 20 Alkyl groups, such as R 4 and R 5 It can be tert-butyl or adamantyl. In at least one embodiment, R 4 and R 5is 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, such as R 4 and R 5 may independently be unsubstituted phenyl or 3,5-di-tert-butylbenzyl. In addition, (1) R 4 Can be C1-C 20 Alkyl (e.g., R 4 may be tert-butyl) and R 5 It may be an aryl group, or (2) R 5 Can be C1-C 20 Alkyl (e.g., R 5 may be tert-butyl) and R 4 It can be an aromatic group. Alternatively, R 4 and / or R 5 can be independently heteroatoms, such as R 4 and R 5 It may be a halogen atom (such as Br, Cl, F or I). 4 and / or R 5 can be independently silyl, for example R 4 and R 5 It can be a trialkylsilyl group or a triarylsilyl group, wherein the alkyl group is C1 to C 30 The alkyl group is C6 to C 1, C7 to C 1, C8 to C9, C9 to C10, C11 to C12, C12 to C13, C14 to C16, C15 to C17, C18 to C19, C19 to C20, C19 to C21, C11 to C22, C12 to C13, C14 to C16, C15 to C18, C19 to C21, C11 to C12, C11 to C13, C12 to C14, C13 to C16, C14 to C18, C15 to C19, C11 to C12, C11 to C13, C12 to C13, C13 to C14, C14 to C16 30 Aryl (e.g., phenyl, benzyl, and naphthyl). Typically, R 4 and R 5 It may be triethylsilyl.

[0051] In some embodiments, R 4 and R 5 Independently C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon groups, more preferably, each R 4 and R 5independently selected from tertiary hydrocarbon groups (e.g., tert-butyl, tert-pentyl, tert-hexyl, tert-heptyl, tert-octyl, tert-nonyl, tert-decyl, tert-undecyl, tert-dodecyl) and cyclic tertiary hydrocarbon groups (e.g., 1-methylcyclohexyl, 1-norbornyl, 1-adamantyl or substituted 1-adamantyl).

[0052] In some embodiments, R 4 and R 5 Independently C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon groups, more preferably, R 4 and R 5 Each of the groups is independently a non-aromatic cyclic alkyl group (e.g., cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, adamantyl, norbornyl or 1-methylcyclohexyl or substituted adamantyl), most preferably a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, 1-adamantyl, substituted 1-adamantyl or 1-norbornyl).

[0053] R 4 and R 5 The nature of can be used to control the molecular weight of the polymer product. For example, when R 4 and R 5 When one or two of the R groups are tert-butyl groups, the catalyst compound can provide a high molecular weight polymer. 4 , R 5 or R 4 and R 5 When phenyl, the catalyst compound can provide a low molecular weight polymer.

[0054] R of formula (I) or (II) 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 Each of can be independently hydrogen or C1-C 10 Alkyl groups, such as R 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 15 , R 16 , R17 , R 18 and R 19 can independently be 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 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 is hydrogen. Alternatively, R 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 of may independently be hydrogen, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy or trimethylsilyl.

[0055] R of formula (I) 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 or R 16 At least one of them independently contains A(R a )(R b )(R c ) in the form of a silyl or germanyl group, wherein A is Si or Ge, and R a , R b and R c Each of C1-C 40 Hydrocarbon or C1-C 40substituted hydrocarbon groups, such as methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, iso-pentyl, iso-amyl, neopentyl, cyclopentyl), hexyl (e.g., n-hexyl, isohexyl, cyclohexyl), heptyl (e.g., n-heptyl, isoheptyl, norbornyl), octyl (e.g., n-octyl, isooctyl, cyclooctyl), nonyl (e.g., n-nonyl, isononyl), decyl (e.g., n-decyl, isodecyl, cyclodecyl, adamantyl), undecyl (e.g., n-undecyl, iso-undecyl), dodecyl (e.g., n-dodecyl, isododecyl, cyclododecyl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, triacontyl, and all isomers thereof, or R a and R b , R a and R c or R b and R c One or more pairs of A(R) may be linked to form one or more substituted hydrocarbyl rings or unsubstituted hydrocarbyl rings. a )(R b )(R c ) is selected from trimethylsilyl, triethylsilyl, tri(n-propyl)silyl, tri(n-butyl)silyl or tri(n-hexyl)silyl.

[0056] In some embodiments, R of formula (I) 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 or R 16 At least one of them is independently A(R a )(R b )(R c ) in the form of a silyl or germanyl group.

[0057] In some embodiments, R of formula (I) 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9 , R10 , R 11 , R 12 , R 13 , R 14 , R 15 or R 16 At least one of them is independently C1-C 120 A substituted hydrocarbon group wherein at least one hydrogen atom of the hydrocarbon group has been replaced by A(R a )(R b )(R c ) is substituted with silyl or germanyl in the form of .

[0058] In at least one embodiment, the catalyst compound is one or more of the following:

[0059] In at least one embodiment, one or more different catalyst compounds are present in the catalyst system. One or more different catalyst compounds may be present in the reaction zone where the method(s) described herein are performed. The same activator may be used for the transition metal compound, however, two different activators may be used in combination, such as a non-coordinating anion activator and an aluminoxane.

[0060] Other exemplary embodiments of the present technological advancement include the following. A composition of formula (I), wherein R 4 and R 5 is adamantyl, R 2 and R 7 Independently A(R a )(R b )(R c ) in the form of a silyl or germanyl group, wherein A is Si or Ge. A composition of formula (I), wherein R 4 and R 5 is adamantyl, R 2 and R 7 Independently A(R a )(R b )(R c ) in the form of a silyl group, wherein A is Si, and A(R a )(R b )(R c ) contains at least seven carbon atoms. A composition of formula (I) wherein R 4 and R 5 is adamantyl, R 2 and R 7 Independently A(R a )(R b )(R c) in the form of a silyl group, wherein A is Si, A(R a )(R b )(R c ) contains at least seven carbon atoms, and R a , R b and R c At least one of them is aliphatic (C3-C 40 )alkyl or (C2-C 40 ) heteroalkyl, which contains a linear carbon chain of at least three carbons in length that is terminally bonded to A. The composition of formula (I), wherein R 4 and R 5 is adamantyl, R 2 and R 7 Independently A(R a )(R b )(R c ) in the form of a silyl group, wherein A is Si, A(R a )(R b )(R c ) contains at least seven carbon atoms, and R a , R b and R c At least one of them is aliphatic (C3-C 40 )alkyl or (C2-C 40 ) heteroalkyl, which contains a linear carbon chain of at least four carbons in length terminally bonded to A. The composition of formula (I), wherein R 4 and R 5 is adamantyl, R 2 and R 7 Independently A(R a )(R b )(R c ) in the form of a silyl group, wherein A is Si, A(R a )(R b )(R c ) contains at least seven carbon atoms, and R a , R b and R c At least two of them are aliphatic (C3-C 40 )alkyl or (C2-C 40 ) heteroalkyl, which contains a linear carbon chain of at least three carbons in length that is terminally bonded to A. The composition of formula (I), wherein R 4 and R 5 is adamantyl, and R 18 Contains A(R a )(R b )(R c ) in the form of a silyl or germanyl group, wherein A is Si or Ge. A composition of formula (I), wherein R 4and R 5 is adamantyl, and R 18 Contains A(R a )(R b )(R c ) in the form of a silyl or germanyl group, wherein A is Si or Ge, and R a , R b and R c At least one of them is aliphatic (C3-C 40 )alkyl or (C2-C 40 ) heteroalkyl containing a linear carbon chain of at least three carbons in length bonded to A at one end.

[0061] Other exemplary embodiments of the present technological advancement include the following. A composition of formula (II), wherein R 4 and R 5 is adamantyl, A' and A" are Si, A'(R a )(R b )(R c ) contains at least 7 carbons, and A”(R e )(R f )(R g ) contains at least 7 carbon atoms. A composition of formula (II) wherein R 4 and R 5 is adamantyl, A' and A" are Si, A'(R a )(R b )(R c ) contains at least seven carbon atoms, R a , R b and R c At least one of them is aliphatic (C3-C 40 )alkyl or (C2-C 40 ) heteroalkyl, which contains a linear carbon chain of at least three carbons in length bonded to A', A" (R e )(R f )(R g ) contains at least seven carbon atoms, and R d , R e and R f At least one of them is aliphatic (C3-C 40 )alkyl or (C2-C 40 ) heteroalkyl, which contains a linear carbon chain of at least three carbons in length bonded to A "at the end. The composition of formula (II), wherein R 4 and R 5 is adamantyl, A' and A" are Si, A'(R a )(R b )(R c ) contains at least seven carbon atoms, R a, R b and R c At least one of them is aliphatic (C3-C 40 )alkyl or (C2-C 40 ) heteroalkyl, which contains a linear carbon chain of at least four carbons in length bonded to A', A" (R e )(R f )(R g ) contains at least seven carbon atoms, and R d , R e and R f At least one of them is aliphatic (C3-C 40 )alkyl or (C2-C 40 ) heteroalkyl, which contains a linear carbon chain of at least four carbons in length bonded to A "at the end. The composition of formula (II), wherein R 4 and R 5 is adamantyl, A' and A" are Si, A'(R a )(R b )(R c ) contains at least seven carbon atoms, R a , R b and R c At least two of them are aliphatic (C3-C 40 )alkyl or (C2-C 40 ) heteroalkyl, which contains a linear carbon chain of at least three carbons in length bonded to A', A" (R e )(R f )(R g ) contains at least seven carbon atoms, and R d , R e and R f At least two of them are independently aliphatic (C3-C 40 )alkyl or (C2-C 40 ) heteroalkyl containing a linear carbon chain of at least three carbons in length terminally bonded to A".

[0062] An exemplary embodiment of the present technological advancement may also be a homogeneous solution comprising an aliphatic hydrocarbon solvent and a complex of formula (I) or (II), wherein the concentration of the complex is 0.20 wt % or more (or 0.25 wt % or more, or 0.30 wt % or more, or 0.35 wt % or more, or 0.40 wt % or more, or 0.50 wt % or more, or 1.0 wt % or more, or 2.0 wt % or more). Without wishing to be bound by theory, it is believed that A (R) in formula (I) or (II) a )(R b )(R c The presence of silyl or germanyl groups in the form of ) contributes to the solubility of these complexes in aliphatic solvents.

[0063] Another exemplary embodiment of the present technological advance includes a process for producing a propylene-based polymer, the process comprising: reacting propylene and one or more optional C3-C 40 Olefin polymerization, propylene and one or more optional C3-C 40 An olefin is contacted with a catalyst system comprising a composition of formula (I) or (II) in one or more continuously 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-based polymer.

[0064] Another exemplary embodiment of the present technological advance includes a process for producing an ethylene-based polymer, the process comprising: reacting ethylene and one or more optional C4-C 40 Olefin polymerization, ethylene and one or more optional C4-C 40 An olefin is contacted with a catalyst system comprising a composition of formula (I) or (II) in one or more continuously 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-based or ethylene-based polymer. Activators and optional scavengers, co-activators and chain transfer agents

[0065] U.S. Patent Application Serial No. 16 / 788,088 (published as US 2020 / 0254431) describes activators, optional scavengers, optional co-activators, and optional chain transfer agents that can be used with the present technology advancement. Particularly useful activators are also described in PCT Application No. 2020 / 044865 (published as WO 2021 / 086467), U.S. Patent Application Serial No. 16 / 394,174 (published as US 2019 / 0330394), and PCT Application No. 2019 / 029056 (published as WO 2019 / 210026), which describes non-aromatic hydrocarbon soluble activator compounds, such as [tetrakis(pentafluorophenyl)boric acid] N-methyl-4-nonadecyl-N-octadecylanilinium, [tetrakis(heptafluoronaphthyl)boric acid] N-methyl-4-nonadecyl-N-octadecylanilinium, [tetrakis(pentafluorophenyl)boric acid)] N-methyl-N-octadecyl-4-(octadecyloxy)anilinium, [tetrakis(heptafluoronaphthyl)boric acid] N-methyl-N-octadecyl-4-(octadecyloxy)anilinium, [tetrakis(pentafluorophenyl)boric acid] N,N-di( Hydrogenated tallow) methylammonium, [tetrakis(heptafluoronaphthyl)borate] N,N-di(hydrogenated tallow) methylammonium, [tetrakis(pentafluorophenyl)borate] N,N-di(octadecyl)methylammonium [tetrakis(heptafluoronaphthyl)borate], [tetrakis(pentafluorophenyl)borate] N,N-di(octadecyl)methylammonium [tetrakis(heptafluoronaphthyl)borate], [tetrakis(pentafluorophenyl)borate] N,N-di(hexadecyl)methylammonium [tetrakis(heptafluoronaphthyl)borate], [tetrakis(pentafluorophenyl)borate] N,N-di(hexadecyl)methylammonium [tetrakis(pentafluorophenyl)borate] N-octadecyl-N-hexadecylmethylammonium [tetrakis(pentafluorophenyl)borate] and [tetrakis(heptafluoronaphthyl)borate] N-octadecyl-N-hexadecylmethylammonium.

[0066] Although it is preferred to use an activator that is soluble in a non-aromatic hydrocarbon solvent, activators that are poorly soluble or insoluble in a non-aromatic hydrocarbon solvent may also be used. When used, these activators can be fed to the reactor via a slurry or as a solid. Particularly useful activators in this class include triphenylcarbon tetrakis(pentafluorophenyl)borate, Triphenylcarbon tetrakis(perfluoronaphthyl)borate N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, etc.

[0067] Typical activator to catalyst ratios are about 1:1 molar ratios. Alternative preferred ranges include 0.1:1-100:1, or 0.5:1-200:1, or 1:1-500:1, or 1:1-1000:1. Particularly useful ranges are 0.5:1 to 10:1, preferably 1:1 to 1:10.

[0068] Particularly useful optional scavengers or co-activators or chain transfer agents include, for example, trialkylaluminums such as triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and dialkylzincs such as diethylzinc. In addition, hydrocarbon-soluble aluminoxanes and modified aluminoxanes that do not contain toluene, including "trimethylaluminum-free" aluminoxanes, can be used.

[0069] In addition, one of ordinary skill in the art will be able to select suitable known activators (one or more) and optional scavengers or co-activators or chain transfer agents for their particular purpose without undue experimentation. Combinations of various activators may be used. Likewise, combinations of various optional scavengers or co-activators or chain transfer agents may be used. Solvents

[0070] Although the catalyst components of the present technology advancement can be used with aromatic solvents such as toluene, they are preferably absent when the catalyst components are used in the polymerization process. Solvents that can be used to dissolve the catalyst compound, the activator compound, or to combine the catalyst compound and the activator, and / or to introduce the catalyst system or any component thereof into the reactor, and / or to be used in the polymerization process include, but are not limited to, aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or combinations thereof; preferred solvents may include normal paraffins (e.g., Norpar available from ExxonMobil Chemical Company of Houston, TX); TM solvents), isoparaffin solvents (e.g., Isopar available from ExxonMobil Chemical Company of Houston TX), TM solvents), non-aromatic cyclic solvents (e.g., Nappar available from ExxonMobil Chemical Company of Houston, TX) TM solvent) and combinations thereof.

[0071] Preferably, the aliphatic hydrocarbon solvent is selected from C4 to C 10 Linear, branched or cyclic alkanes, or selected from C5 to C8 linear, branched or cyclic alkanes.

[0072] Preferably, the aliphatic hydrocarbon solvent is substantially free of all aromatic solvents. Preferably, the solvent is substantially free of toluene. Free of all aromatic solvents, such as toluene, means that the solvent is substantially free of aromatic solvents (e.g., present at 0 mol %, or present at less than 1 mol %), preferably, the polymerization reaction and / or the resulting polymer does not contain "detectable aromatic hydrocarbon solvents", such as toluene.

[0073] Preferred aliphatic hydrocarbon solvents include isohexane, cyclohexane, methylcyclohexane, pentane, isopentane, heptane, and combinations thereof, as well as commercially available solvent mixtures such as Nappar 6 TM and IsoparE TM However, one of ordinary skill in the art may select other suitable non-aromatic hydrocarbon solvents without undue experimentation.

[0074] Highly preferred aliphatic hydrocarbon solvents include isohexane, methylcyclohexane and commercially available solvent mixtures such as Nappa 6 TM and IsoparE TM .

[0075] For compound solubility testing, preferred solvents include isohexane and methylcyclohexane. Optional carrier material

[0076] In the embodiments herein, the catalyst system may include an inert support material. The support material may be a porous support material, for example, talc, and an inorganic oxide. U.S. Patent Application Serial No. 16 / 788,088 (Publication No. US2020 / 0254431) describes optional support materials that can be used with this technological advancement. In addition, one of ordinary skill in the art can select a suitable known support for its specific purpose without excessive experimentation. Aggregation methods

[0077] The present disclosure relates to a polymerization process wherein monomers (e.g., ethylene; propylene) and optionally one or more comonomers (e.g., C2 to C 20 α-olefins, C4 to C 40 Cyclic olefins, C5 to C 20 The catalyst system of the present invention is a catalyst system comprising an activator and at least one catalyst compound as described above. The catalyst compound and the activator can be combined in any order. The catalyst compound and the activator can be combined before contacting with the monomer. Alternatively, the catalyst compound and the activator can be introduced separately into a polymerization reactor, where they are subsequently reacted to form an active catalyst.

[0078] U.S. patent application Ser. No. 16 / 788,088 (Pub. No. US 2020 / 0254431) describes monomers that can be used in the present technological advancement, and describes polymerization methods that can be used in the present technological advancement.

[0079] Additionally, catalysts that are highly soluble in aliphatic hydrocarbon solvents can be used as trim catalysts in well-known polymerization processes, such as described in WO 2015 / 123177 and WO 2020 / 092587. blends and films

[0080] Polymers prepared using this technological advance can be used to prepare blends and films as described in U.S. Patent Application Serial No. 16 / 788,088 (Publication No. US2020 / 0254431) without undue experimentation. Example General considerations for synthesis

[0081] The following chemicals can be abbreviated with lowercase or uppercase letters: 1,2-dimethoxyethane (dme), diethyl ether (ether), tetrahydrofuran (thf), diatomaceous earth (Celite), methylcyclohexane (MeCy), 1,4-dimethoxyethane (dme), diethyl ether (ether), tetrahydrofuran (thf), diatomaceous earth (Celite), methylcyclohexane (MeCy), Alkane (di alkane), hexamethyldisiloxane (HMDSO), N,N-dimethylformamide (DMF), N-bromosuccinimide (NBS), n-butyllithium (n-BuLi), tert-butyllithium (t-BuLi). Room temperature is 23°C unless otherwise specified.

[0082] Complexes 1 and 2 (shown below) were prepared as described in U.S. Patent Application US 2020 / 0255553 A1.

[0083] All other reagents were purchased from commercial suppliers (Sigma Aldrich, Fisher Scientific, Strem Chemical, or Oakwood Chemical) and used as received unless otherwise stated. The solvents were sparged with N2 and All chemical manipulations were performed under nitrogen atmosphere unless otherwise stated. Flash column chromatography was performed using silica gel from Sigma Aldrich (70 mesh - 230 mesh) using the specified solvent system. All anhydrous solvents were purchased from Fisher Chemical and degassed and dried over molecular sieves before use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and degassed and dried over molecular sieves before use. Solutions prepared by dissolving approximately 10 mg of sample in C6D6, CD2Cl2, CDCl3, D8-toluene or other deuterated solvents were used and obtained at 250 MHz, 400 MHz or 500 MHz. 1 H NMR spectral data. The chemical shifts (δ) presented are relative to the residual protium in the deuterated solvent at 7.15 ppm, 5.32 ppm, 7.24 ppm and 2.09 ppm for C6D6, CD2Cl2, CDCl3, D8-toluene, respectively. Synthesis of ligands and catalysts

[0084] ZrCl4 (ether) 2. Combine dichloromethane (100 mL) and ZrCl4 (10.0 g, 42.9 mmol) to form a slurry. Add ether (9.54 g, 129 mmol) dropwise over 60 minutes. Stir the mixture for 1 hour. Allow the undissolved solid to settle, then decant the supernatant and filter through Celite on a sintered disk. Evaporate the filtrate to near dryness to provide a slurry. Add isohexane (60 mL) to the slurry and stir the mixture vigorously. The resulting off-white solid is collected on a frit, washed with isohexane, and dried under reduced pressure. Yield: 12.5 g, 76.6%. Adamantyl aryl precursor

[0085] 2-(1-adamantyl)-4-bromophenol To a solution of 1-adamantanol (26.5 g, 174 mmol) and 4-bromophenol (30.2 g, 174 mmol) in dichloromethane (50 mL) was added 98% sulfuric acid (24.4 g, 249 mmol) at 0°C. The reaction was stirred at 0°C for 1.5 hours and then at ambient temperature for 0.5 hours. The reactant was diluted with dichloromethane (200 mL) and then slowly quenched with aqueous Na2CO3 solution (~100 mL). After the mixture was stirred for 30 minutes, the aqueous phase was separated and extracted with additional dichloromethane. The organic extracts were combined, dried over MgSO4, filtered and concentrated to dryness. The crude product was slurried in pentane (50 mL) and then cooled at -20°C for 1 hour. The mixture was filtered to give the desired compound as a white solid (47.0 g, 88%). 1 HNMR (400MHz, CDCl3) δ7.32 (s, 1H), 7.18 (d, J = 8.3Hz, 1H), 6.55 (d, J = 8.4Hz, 1H), 4.74 (s, 1H), 2.11 (s, 9H), 1.80 (s, 6H).

[0086] 1-(5-Bromo-2-(methoxymethoxy)phenyl)adamantane To a solution of 2-(1-adamantyl)-4-bromophenol (15.0 g, 48.8 mmol) in diethyl ether (80 mL) was added sodium hydride (1.37 g, 51 mmol) at ambient temperature. The reaction was stirred for 3 hours and then concentrated to dryness. The crude product was diluted with pentane (50 mL). The resulting mixture was stirred for 30 minutes and then filtered to obtain the sodium aryloxide intermediate as a white solid.

[0087] To a solution of the sodium phenol intermediate in THF (50 mL) was added methoxymethyl bromide (5.33 g, 43 mmol). The reaction was stirred for 3 hours and then concentrated to remove most of the THF. The crude product was diluted with dichloromethane (30 mL) and washed with water. The aqueous phase was separated and extracted with additional dichloromethane. The organic extracts were combined, dried over MgSO4, filtered and concentrated to dryness to give the product as a yellow solid (12.8 g, 75%). 1 H NMR (400MHz, CDCl3) δ7.34 (s, 1H), 7.26 (d, J = 8.8Hz, 1H), 7.00 (d, J = 8.6Hz, 1H), 5.22 (s, 2H), 3.53 (d, J = 1.2Hz, 3H), 2.10 (s, 9H), 1.79 (s, 6H).

[0088] 2-(2-(1-adamantyl)-4-bromophenoxy)tetrahydro-2H-pyran To a solution of 2-(1-adamantyl)-4-bromophenol (3.30 g, 10.7 mmol) and 3,4-dihydro-2H-pyran (2.71 g, 32.2 mmol) in dichloromethane (10 mL) was added p-toluenesulfonic acid monohydrate (20.4 mg, 0.1 mmol) at 0°C. The reaction mixture was stirred at 0°C for 45 minutes. The reactants were poured into a 1M NaOH aqueous solution (10 mL) and the resulting mixture was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was stirred in methanol for 2 hours. The product was isolated by filtration as a yellow solid (3.60 g, 86%). 1 H NMR (400MHz, CDCl3) δ7.30(d,J=2.1Hz,1H),7.23(d,J=8.7Hz,1H),7.05(d,J=8.7Hz,1H),5.43(s,1H) ,3.86(t,J=9.6Hz,1H),3.65(d,J=12.0Hz,1H),2.09(br,9H),1.97-1.89(m,2H),1.84-1.36(m,10H).

[0089] (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)trimethylsilane To a solution of 10.0 g (28.5 mmol) of 1-(5-bromo-2-(methoxymethoxy)phenyl)adamantane in 150 mL of dry THF was added 13.7 mL (34.2 mmol) of 2.5 M n-BuLi in hexanes dropwise over 30 minutes at -80°C. The reaction mixture was stirred at this temperature for 1 hour, then 4.33 g (39.9 mmol) of chlorotrimethylsilane was added. The resulting solution was stirred at room temperature for 1 hour, then poured into 300 mL of water. The crude product was extracted with dichloromethane (3 x 100 mL); the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. 9.69 g (99%) of a white solid was produced. 1 H NMR (CDCl3, 400MHz): δ7.46 (d, J=1.6Hz, 1H), 7.38 (dd, J=8.1, 1.6Hz, 1H), 7.16 (d, J=8.1H z,1H),5.30(s,2H),3.57(s,3H),2.20-2.22(m,6H),2.14(br.s,3H),1.80-1.90(m,6H),0.32(s,9H). 13 C NMR (CDCl3, 100MHz): δ157.1, 137.5, 132.3, 131.9, 131.6, 113.8, 94.0, 56.2, 40.6, 37.1, 29.1, -0.9.

[0090] (3-(1-adamantyl)-4-(methoxymethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)trimethylsilane To a solution of 9.66 g (28.0 mmol) of (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)trimethylsilane in 450 mL of diethyl ether was added dropwise 16.8 mL (42.1 mmol) of 2.5 M n-BuLi in hexane at 0° C. over 20 minutes. The reaction mixture was stirred at room temperature for 12 hours and then cooled to −80° C., followed by the addition of 11.5 mL (56.1 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The obtained mixture was extracted with dichloromethane (3×300 mL); the combined organic extracts were dried over Na 2 SO 4 and then evaporated to dryness. 12.9 g (98%) of a white solid were produced. 1H NMR (CDCl3, 400MHz): δ7.69 (d, J = 1.7Hz, 1H), 7.54 (d, J = 1.7Hz, 1H), 5.22 (s, 2H), 3.60 (s ,3H),2.17-2.20(m,6H),2.10(br.s,3H),1.76-1.84(m,6H),1.37(s,12H),0.27(s,9H). 13 C NMR (CDCl3, 100MHz): δ162.8,140.1,139.7,135.1,133.2,100.7,83.6,57.8,41.1,37.2,37.1,29.1,24.8,-0.9.

[0091] (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)trimethylsilane Then, 5.00 g (10.6 mmol) of (3-(1-adamantyl)-4-(methoxymethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)trimethylsilane was added to 30 mL of 1,4-dioxaborolan-2-yl. 3.00 g (10.6 mmol) of 2-bromoiodobenzene, 8.66 g (26.6 mmol) of cesium carbonate and 15 mL of water were added to the solution in oxane. The obtained mixture was purged with argon for 10 minutes, and then 614 mg (0.531 mmol) of Pd(PPh3)4 was added. This mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 100 ml of water. The obtained mixture was extracted with dichloromethane (3×100 mL); the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane=10:1, volume). 2.44 g (46%) of white solid was produced. 1 H NMR (CDCl3, 400MHz): δ7.71 (d, J = 7.3Hz, 1H), 7.51 (d, J = 1.5Hz, 1H), 7.35-7.45 (m, 2H), 7.20-7.26 (m, 2H), 4.56 (d, J = 4. 6Hz, 1H, AB), 4.48 (d, J = 4.6Hz, 1H, AB), 3.26 (s, 3H), 2.21-2.24 (m, 6H), 2.14 (br.s, 3H), 1.79-1.86 (m, 6H), 0.30 (s, 9H). 13C NMR (CDCl3, 100MHz): δ154.7,141.9,141.3,135.1,134.1,134.0,133.0,13 2.3,131.8,128.7,127.1,124.2,98.9,57.2,41.2,37.4,37.0,29.1,-0.9.

[0092] (4-(1-adamantyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinin-2-yl)trimethylsilane To a solution of 2.44 g (4.88 mmol) of (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)trimethylsilane in 50 mL of dry THF was added dropwise 2.3 mL (5.86 mmol) of 2.5 M n-BuLi in hexane at -80°C over 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 1.49 mL (7.33 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The obtained suspension was stirred at room temperature for 1 hour, then poured into 300 mL of water. This mixture was extracted with dichloromethane (3 x 100 mL); the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. 50 mL of isopropanol were added to the residue, and the resulting solution was refluxed for 2 hours. After cooling to room temperature, the precipitate formed was filtered off on a glass frit (G4), washed with 5 mL of cold isopropanol and then dried under vacuum. Yield: 2.21 g (96%) of a white solid. 1 H NMR (CDCl3, 400MHz): δ8.25(s,1H),8.24(d,J=8.4Hz,1H),8.10(d,J=8.4Hz,1H),7.69(t,J=8.4Hz,1H),7.55(s,1H),7.45(t,J= 7.4Hz,1H),5.30(sept,J=6.2Hz,1H),2.34-2.36(m,6H),2.20(br.s,3H),1.86-1.90(m,6H),1.46(d,J=6.2Hz,6H),0.39(s,9H). 13 C NMR (CDCl3, 100MHz): δ151.2,140.6,138.6,133.0,132.5,131.9,131.2,127.1,126.7,122.5,121.6,65.8,40.7,37.3,37.1,29.1,24.8,-0.8.

[0093] 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(trimethylsilyl)-[1,1'-biphenyl]-2-phenol) Then, 2.21 g (4.87 mmol) of (4-(1-adamantyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborin-2-yl)trimethylsilane was added to 12 mL of 1,4-dihydro-1,4-diol. To a solution of 1,559 mg (2.36 mmol) of 2,6-dibromopyridine, 4.05 g (12.4 mmol) of cesium carbonate and 6 mL of water were added. The obtained mixture was purged with argon for 10 minutes, and then 287 mg (0.25 mmol) of Pd(PPh3)4 was added. This mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The obtained mixture was extracted with dichloromethane (3×50 mL); the combined organic extracts were dried over Na2SO4 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, volume). 910 mg (46%) of a mixture of two isomers was produced as a white powder. 1 H NMR (CDCl3, 400 MHz): δ 8.32 (s, 2H in A), 7.35-7.53 (m, 9H in A and B), 7.20 (d, J = 1.3 Hz, 2H in A), 7.14 (d, J = 1.3 Hz, 2H in B), 7.06 (d, J = 7.8 Hz, 2H in B), 7.03 (s, 2H in B), 7.01 (d, J = 7.8 Hz, 2H in A), 6.69 (d, J = 1.3 Hz, 2H in A), 1.60-2.02 (m, 30H in A and B), 0.15 (s, 18H in B), 0.00 (s, 18H in A). 13 C NMR (CDCl3, 100 MHz, A only) δ 157.8, 153.4, 139.4, 137.5, 134.7, 131.8, 130.9, 130.8, 130.1, 129.9, 129.0, 127.8, 122.5, 40.4, 37.0, 36.9, 29.1, -0.9.

[0094] (3-(1-adamantyl)-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)triethylsilane To a solution of 2-(2-(1-adamantyl)-4-bromophenoxy)tetrahydro-2H-pyran (4.66 g, 11.9 mmol) and chlorotriethylsilane (3.59 g, 23.8 mmol) in THF (10 mL) was added magnesium powder (34.7 mg, 14 mmol). A minimum amount of iodine was added to initiate the reaction. The reaction mixture was refluxed for 16 hours and then concentrated to dryness. The crude mixture was slurried in hexane / dichloromethane (50:50). The solids were then removed by filtration and the filtrate was concentrated to dryness. The residue was purified by flash chromatography on silica gel (10% dichloromethane in hexane) to give the product as a clear oil (1.39 g, 27%). 1 H NMR (400MHz, CDCl3) δ7.34(s,1H),7.27(d,J=9.9Hz,1H),7.15(d,J=8.1Hz,1H),5.51(s,1H),3.92(t,J=10.3Hz,1H),3.66 (d,J=11.7Hz,1H),2.27-2.01(m,10H),2.00-1.87(m,2H),1.83-1.60(m,9H),0.97(t,J=7.9Hz,9H),0.76(q,J=7.9Hz,6H).

[0095] (5-(1-adamantyl)-2'-bromo-6-((tetrahydro-2H-pyran-2-yl)oxy)-[1,1'-biphenyl]-3-yl)triethylsilane To a solution of (3-(1-adamantyl)-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)triethylsilane (1.82 g, 4.3 mmol) in diethyl ether (10 mL) was added n-BuLi (11 M, 0.43 mL, 4.7 mmol) in hexanes at ambient temperature. The solution was stirred for 1 hour and then concentrated to dryness. The lithiated intermediate was dissolved in hexanes. To the resulting solution was added 2-bromochlorobenzene (0.86 g, 4.5 mmol) in hexanes (1 mL) dropwise at 60°C. The reaction was stirred at 60°C for 1 hour and then filtered through Celite. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (10% dichloromethane in hexanes) to give the product as a foamy solid (2.24 g, 100%). 1H NMR (400MHz, CDCl3) δ7.66(dd,J=30.4,8.0Hz,1H),7.45-7.28(m,3H),7.24-7.16(m,1H),7.06(d,J=57.3Hz,1H),4.32(d,J=8.1Hz,1H),3.77(dd,J =41.1,12.0Hz,1H),2.96(dt,J=99.6,11.1Hz,1H),2.34-1.99(m,9H),1. 82-1.61(m,8H),1.47-1.06(m,4H),1.05-0.91(m,9H),0.82-0.68(m,6H).

[0096] 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(triethylsilyl)-[1,1'-biphenyl]-2-phenol) To a solution of (5-(1-adamantyl)-2'-bromo-6-((tetrahydro-2H-pyran-2-yl)oxy)-[1,1'-biphenyl]-3-yl)triethylsilane (2.24 g, 3.8 mmol) in THF (10 mL) was added n-BuLi (11 M, 0.35 mL, 3.8 mmol) in hexanes at ambient temperature. The solution was stirred for 1 hour. Zinc dichloride (0.49 g, 3.6 mmol) was then added and the reaction mixture was stirred for 10 minutes. 2,6-dibromopyridine (0.34 g, 1.4 mmol) and Pd (P t The reaction mixture was stirred at 70 ° C for 16 hours and then cooled to ambient temperature. Then 1M HCl (1mL) was added and the reaction mixture was stirred for 16 hours. The mixture was diluted with water and extracted with dichloromethane (3×10mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was purified on silica gel by flash chromatography (eluting impurities with 20% dichloromethane in hexane, and then eluting the product with 20% dichloromethane + 10% EtOAc in hexane). The product was then dissolved in diethyl ether (~1mL) and hexane (5mL) was subsequently added. The resulting mixture was cooled to -20 ° C for 16 hours. The product was isolated by filtration as a white solid (0.316g, 9.7%). 1H NMR (400MHz, CDCl3) δ7.78(t,J=8.0Hz,1H),7.63(d,J=7.6Hz,4H),7.44(t,J=7.4Hz,2H),7.26(d,J=3.4Hz,4H),7.17(d,J=7.9H z,2H),7.01(d,J=7.8Hz,2H),6.84(s,2H),2.03(br,12H),1.76(br,8H),1.26(br,10H),0.99-0.79(m,18H),0.70-0.57(m,12H).

[0097] (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)tripropylsilane To a solution of 1-(5-bromo-2-(methoxymethoxy)phenyl)adamantane (2.19 g, 6.23 mmol) in THF (5 mL) was added t-BuLi (1.7 M, 7.3 mL, 12.5 mmol) in pentane at -60°C over 10 minutes. The reaction mixture was stirred at -60°C for 1 hour, then tripropylsilyl chloride (1.20 g, 6.23 mmol) was added. The solution was stirred at -60°C for 30 minutes, then stirred at ambient temperature for 1 hour. The reaction was poured into water (10 mL), and the resulting mixture was extracted with dichloromethane (3 x 100 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel (10% dichloromethane in hexanes) to give the product as a foamy solid (1.68 g, 63%). 1 H NMR(400MHz, CDCl3) δ7.32(d,J=1.7Hz,1H),7.26-7.24(m,1H),7.05(d,J=8.0Hz,1H),5.23(s,2H),3.5 2(s,3H),2.23-2.00(m,9H),1.79(br,6H),1.41-1.30(m,6H),0.96(t,J=7.2Hz,9H),0.80-0.70(m,6H).

[0098] (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)tripropylsilane To a solution of (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)tripropylsilane (1.68 g, 3.9 mmol) in diethyl ether (10 mL) was added n-BuLi (1.6 M, 2.5 mL, 3.9 mmol) in hexanes at ambient temperature. The solution was stirred for 1 hour and then concentrated to dryness. The lithiated intermediate was dissolved in hexanes. To the resulting solution was added dropwise 2-bromochlorobenzene (0.79 g, 4.1 mmol) in hexanes (1 mL) at 60°C. The reactants were stirred at 60°C for 1 hour and then filtered through Celite. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (10% dichloromethane in hexanes) to give the product as a foamy solid (1.98 g, 87%). 1 H NMR (400MHz, CDCl3) δ7.70(dd,J=8.0,1.2Hz,1H),7.44-7.40(m,2H),7.37(td,J=7.4,1.2Hz,1H),7.23(ddd,J=8.1,7.2,2.0Hz,1H),7.17(d,J=1.6Hz, 1H),4.49(dd,J=54.8,4.7Hz,2H),3.24(s,3H),2.32-2.03(m,9H),1.82(d, J=3.4Hz, 6H), 1.50-1.32 (m, 6H), 0.98 (t, J=7.2Hz, 9H), 0.83-0.75 (m, 6H).

[0099] (4-(1-adamantyl)-6-isopropoxy-benzo[c][1,2]benzoxaborin-2-yl)tripropylsilane To a solution of (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)tripropylsilane (1.98 g, 3.4 mmol) in THF (5 mL) was added n-BuLi (2.5 M, 1.50 mL, 3.7 mmol) in hexanes at -60 °C over 10 minutes. The reaction mixture was stirred at -60 °C for 1 hour, then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.95 g, 5.1 mmol) was added. The resulting suspension was stirred at ambient temperature for 1 hour, then poured into 5 mL of water. The resulting mixture was extracted with dichloromethane (3 x 5 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness.

[0100] Isopropanol (20 mL) was added to the residue and the resulting solution was refluxed for 16 hours. After the reaction was allowed to cool to ambient temperature, the reaction was concentrated to dryness. The product was washed with cold isopropanol and isolated as a white solid (1.46 g, 81%). 1 HNMR (500 MHz, CDCl3) δ8.31-8.12 (m, 2H), 8.06 (d, J = 6.9 Hz, 1H), 7.69 (dt, J = 28.4, 7.8 Hz, 1H), 7.50-7.35 (m, 2H), 5.25 (q, J = 6.2 Hz, 1H in A), 4.03 (q, J = 6.0 Hz, 1H in A), 2.36-2.10 (m, 9H), 1.85 (br, 6H), 1.49-1.34 (m, 9H), 1.22 (d, J = 6.1 Hz, 3H), 1.00 (td, J = 7.3, 1.8 Hz, 9H), 0.89-0.78 (m, 6H).

[0101] 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tripropylsilyl)-[1,1'-biphenyl]-2-phenol) To a solution of (4-(1-adamantyl)-6-hydroxy-benzo[c][1,2]benzooxaborinane-2-yl)tripropylsilane (1.42 g, 2.9 mmol) in THF (8 mL) was then added 2,6-dibromopyridine (0.34 g, 1.45 mmol), potassium carbonate (1.21 g, 8.7 mmol), Buchwald RuPhos Palladacycle Gen I precatalyst (Strem, CAS1028206-60-1, 10.6 mg, 0.01 mmol,) and water (2 mL). The reaction mixture was stirred at 90 ° C for 16 hours, then cooled to ambient temperature and diluted with water (5 mL). The obtained mixture was extracted with dichloromethane (3×10 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel (eluting the impurities with 20% dichloromethane in hexanes, then eluting the product with 20% dichloromethane + 10% EtOAc in hexanes). The product was isolated as a mixture of two isomers as a foamy solid (1.05 g, 79%). 1H NMR (400 MHz, CDCl3) δ 7.77 (s, 2H in A), 7.54-7.34 (m, 9H), 7.19-7.14 (m, 2H), 6.99 (d, J = 7.8 Hz, 2H in A), 6.94 (d, J = 1.5 Hz, 2H in B), 6.91 (d, J = 7.8 Hz, 2H in B), 6.74 (d, J = 1.6 Hz, 2H in A), 6.32 (s, 2H in B), 2.01-1.88 (m, 18H), 1.78-1.56 (m, 12H), 1.33-1.09 (m, 12H), 0.87 (t, J = 7.3 Hz, 18H), 0.69-0.36 (m, 12H).

[0102] (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)tributylsilane To a solution of 1-(5-bromo-2-(methoxymethoxy)phenyl)adamantane (5.07 g, 14.4 mmol) in THF (30 mL) was added t-BuLi (1.7 M, 17.0 mL, 28.8 mmol) in pentane at -55°C over 10 minutes. The reaction mixture was stirred at -55°C for 1 hour, then tributylsilyl chloride (3.39 g, 14.4 mmol) was added. The solution was stirred at -55°C for 30 minutes, then at ambient temperature for 1 hour. The reactants were poured into water (50 mL), and the resulting mixture was extracted with dichloromethane (3 x 100 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The product was isolated as a clear oil (6.80 g, quantitative yield). 1 H NMR (400MHz, CDCl3) δ7.34(d,J=1.6Hz,1H),7.26(dd,J=8.0,1.6Hz,1H),7.06(d,J=8.1Hz,1H),5.23(s,2H),3.53(s ,3H),2.15-2.05(m,J=17.3,3.5Hz,9H),1.78(s,6H),1.38-1.26(m,12H),0.88(t,J=6.8Hz,9H),0.79-0.70(m,6H).

[0103] (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)tributylsilane To a solution of (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)tributylsilane (6.80 g, 14.4 mmol) in diethyl ether (50 mL) was added n-BuLi (1.6 M, 9.0 mL, 14.4 mmol) in hexanes at ambient temperature. The solution was stirred for 1 hour and then concentrated to dryness. The lithiated intermediate was dissolved in hexanes. To the resulting solution was added dropwise 2-bromochlorobenzene (3.18 g, 16.6 mmol) in hexanes (5 mL) at 60°C. The reaction was stirred at 60°C for 1 hour and then filtered through Celite. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (10% dichloromethane in hexanes) to give the product as a foamy solid (5.64 g, 63%). 1 H NMR (400MHz, CDCl3) δ7.68(d,J=8.0Hz,1H),7.44-7.29(m,3H),7.20(t,J=7.7Hz,1H),7.15(s,1H),4.55(d,J=4.7Hz,1H),4.40(d,J=4 .7Hz,1H),3.22(d,J=1.2Hz,3H),2.22-2.02(m,9H),1.79(s,6H),1.35-1.28(m,12H),0.94-0.81(m,9H),0.79-0.72(d,J=9.3Hz,6H).

[0104] (4-(1-adamantyl)-6-hydroxy-benzo[c][1,2]benzoxaborin-2-yl)tributylsilane To a solution of (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)tributylsilane (5.64 g, 8.5 mmol) in THF (30 mL) was added n-BuLi (2.5 M, 3.73 mL, 9.3 mmol) in hexanes at -68 °C over 10 minutes. The reaction mixture was stirred at -68 °C for 1 hour, then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.36 g, 12.7 mmol) was added. The resulting suspension was stirred at ambient temperature for 1 hour, then poured into 50 mL of water. The resulting mixture was extracted with dichloromethane (3 x 100 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness.

[0105] Isopropyl alcohol (40mL) was added to the residue, and the resulting solution was refluxed for 3 hours. After the reaction was cooled to ambient temperature, the reactant was concentrated to dryness. The product was purified on silica gel by flash chromatography (using 20% ​​dichloromethane in hexane to elute impurities, then 20% dichloromethane in hexane + 20% EtOAc to elute the product). The isolated product was a foamy solid (2.58 g, 58%). 1 H NMR (400MHz, CDCl3) δ8.33-8.14(m,2H),8.08(dd,J=18.9,7.5Hz,1H),7.73(dt,J=15.3,7.6Hz,1H),7.48-7.40(m ,2H),4.57(s,1H),2.35-2.11(m,6H),2.08(br,s,3H),1.87-1.74(m,6H),1.41-1.29(m,12H),0.93-0.81(m,15H).

[0106] 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tributylsilyl)-[1,1'-biphenyl]-2-phenol) Then, (4-(1-adamantyl)-6-hydroxy-benzo[c][1,2]benzoxaborin-2-yl)tributylsilane (2.50 g, 4.73 mmol) was added to 1,4-dihydro- A solution of 2,6-dibromopyridine (0.56 g, 2.36 mmol), potassium carbonate (1.96 g, 14.2 mmol), Buchwald RuPhos Palladacycle Gen I precatalyst (Strem, CAS 1028206-60-1, 17.2 mg, 0.02 mmol) and water (15 mL) were added. This mixture was stirred at 100°C for 16 hours, then cooled to ambient temperature and diluted with water (30 mL). The obtained mixture was extracted with dichloromethane (3×50 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was purified on silica gel by flash chromatography (eluting the impurities with 20% dichloromethane in hexane, then eluting the residue with 20% dichloromethane + 20% EtOAc in hexane). The product was isolated as a mixture of two isomers as a foamy solid (2.48 g, 97%). 1HNMR (400 MHz, CDCl3) δ 7.51-7.35 (m, 9H), 7.34 (s, 2H in A), 7.22 (s, 2H in B), 7.18 (s, 2H in A), 7.02 (d, J = 7.8 Hz, 2H in A), 6.98 (d, J = 1.4 Hz, 2H in B), 6.93 (d, J = 7.8 Hz, 2H in B), 6.78 (d, J = 1.4 Hz, 2H in A), 6.41 (s, 2H in B), 2.05-1.88 (m, 18H), 1.71 (s, 12H), 1.38-1.13 (m, 24H), 0.86 (t, J = 7.1 Hz, 18H), 0.74-0.50 (m, 12H).

[0107] (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)triisopropylsilane To a solution of 14.0 g (39.8 mmol) of 1-(5-bromo-2-(methoxymethoxy)phenyl)adamantane in 300 ml of dry THF was added dropwise 45.4 mL (81.7 mmol) of 1.8 M t-BuLi in pentane at -80°C over 30 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 9.22 g (47.8 mmol) of triisopropylsilyl chloride was added. The resulting solution was stirred at room temperature for 1 hour, then poured into 300 mL of water. The obtained mixture was extracted with dichloromethane (3 x 100 mL); the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. 16.2 g (95%) of an off-white solid were produced. 1 H NMR (CDCl3, 400MHz): δ7.41 (d, J=1.5Hz, 1H), 7.34 (dd, J=8.1, 1.5Hz, 1H), 7.13 (d, J=8.1Hz, 1H), 5.30 (s, 2H), 3.5 9(s,3H),2.18-2.23(m,6H),2.15(br.s,3H),1.84-1.88(m,6H),1.44(sept,J=7.5Hz,3H),1.15(d,J=7.5Hz,18H). 13 C NMR (CDCl3, 100MHz): δ156.9,137.0,134.1,133.5,126.0,113.4,94.0,56.2,40.9,37.2,37.1,29.2,18.6,10.9.

[0108] (3-(1-adamantyl)-4-(methoxymethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)triisopropylsilane To a solution of 16.1 g (37.5 mmol) of (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)triisopropylsilane in 300 ml of diethyl ether, 22.6 ml (56.3 mmol) of 2.5 M n-BuLi in hexane were added dropwise at 0° C. over 20 minutes. The reaction mixture was stirred at room temperature for 12 hours and then cooled to −80° C., followed by the addition of 15.3 mL (75.0 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The obtained mixture was extracted with dichloromethane (3×300 mL); the combined organic extracts were dried over Na 2 SO 4 and then evaporated to dryness. The residue was triturated with a small amount of n-hexane. 20.5 g (98%) of a white solid were produced. 1 H NMR (CDCl3, 400MHz): δ7.66(d,J=1.5Hz,1H),7.49(d,J=1.5Hz,1H),5.25(s,2H),3.60(s,3H),2.14-2.21( m,6H),2.10(br.s,3H),1.75-1.85(m,6H),1.40(sept,J=7.5Hz,3H),1.37(s,12H),1.09(d,J=7.5Hz,18H). 13 C NMR (CDCl3, 100MHz): δ162.4,141.6,139.3,136.9,127.3,100.3,83.5,57.6,41.3,37.08,37.05,29.2,24.7,18.6,10.9.

[0109] (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)triisopropylsilane Then, 20.5 g (36.9 mmol) of (3-(1-adamantyl)-4-(methoxymethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)triisopropylsilane was added to 100 mL of 1,4-dioxaborolan-2-yl. In the solution in alkane, 11.5g (40.6mmol) of 2-bromoiodobenzene, 15.3g (111mmol) of potassium carbonate and 50mL of water were added. The obtained mixture was purged with argon for 10 minutes, and then 2.13g (1.85mmol) of Pd (PPh3)4 was added. This mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 100ml of water. The obtained mixture was extracted with dichloromethane (3×100mL). The combined organic extracts were dried on Na2SO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63um, eluent: hexane-dichloromethane=10:1, volume). 8.14g (38%) of white solid was produced. 1 H NMR (CDCl3, 400MHz): δ7.69 (d, J = 8.0 Hz, 1H), 7.40-7.44 (m, 2H), 7.36 (dt, J = 7.3 ,1.1Hz,1H),7.21(dt,J=7.3,1.8Hz,1H),7.16(d,J=1.5Hz,1H),4.58-4.59(m,1H ),4.41-4.42(m,1H),3.24(s,3H),2.16-2.20(m,6H),2.12(br.s,3H),1.75-1.8 6(m,6H),1.39(sept,J=7.5Hz,3H),1.10(d,J=7.5Hz,9H),1.08(d,J=7.5Hz,9H). 13 CNMR(CDCl3,100MHz): δ154.4,141.5,141.4,136.8,133.8,133.7,132.9,132. 4,128.5,128.4,127.1,124.3,98.9,57.2,41.5,37.4,37.0,29.2,18.6,10.9.

[0110] (4-(1-adamantyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborin-2-yl)triisopropylsilane To a solution of 8.14 g (13.9 mmol) of (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)triisopropylsilane in 120 mL of dry THF was added dropwise 5.86 mL (14.6 mmol) of 2.5 M n-BuLi in hexane at -80°C over 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, and then 4.51 mL (20.9 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The obtained suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The obtained mixture was extracted with dichloromethane (3×100 mL). The combined organic extracts were dried over Na2SO4 and then evaporated to dryness. 120 mL of isopropanol were added to the residue and the resulting solution was refluxed for 2 hours. After cooling to room temperature, the formed precipitate was filtered through a glass frit (G4), washed with 10 mL of cold isopropanol and then dried under vacuum. Yield: 7.10 g (96%) of a white solid. 1 H NMR (CDCl3, 400MHz): δ8.20(d,J=1.0Hz,1H),8.17(d,J=8.3Hz,1H),8.08(dd,J=7 .4,1.1Hz,1H),7.66(dt,J=7.0,1.5Hz,1H),7.48(d,J=1.3Hz,1H),7.43(t,J=8.0 Hz,1H),5.27(sept,J=6.1Hz,1H),2.28-2.32(m,6H),2.17(br.s,3H),1.82-1.90 (m,6H),1.49(sept,J=7.5Hz,3H),1.43(d,J=6.1Hz,6H),1.15(d,J=7.5Hz,18H). 13 C NMR (CDCl3, 100MHz): δ151.0,140.8,138.2,133.4,133.1,131.9,128.9,126.9,122.3,121.5,65.8,40.9,37.3,37.2,29.2,24.7,18.7,10.9.

[0111] 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(triisopropylsilyl)-[1,1'-biphenyl]-2-phenol) Then, 7.10 g (13.4 mmol) of (4-(1-adamantyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborin-2-yl)triisopropylsilane was added to 40 mL of 1,4-dihydro-1,4-diol. 1.49 g (6.32 mmol) of 2,6-dibromopyridine, 13.2 g (40.3 mmol) of cesium carbonate and 20 mL of water were added to the solution in oxane. The obtained mixture was purged with argon for 10 minutes, and then 780 mg (0.67 mmol) of Pd(PPh3)4 was added. This mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The obtained mixture was extracted with dichloromethane (3×50 mL); the combined organic extracts were dried over Na2SO4 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, volume). 4.50 g (69%) of a mixture of two isomers was produced as a white powder. 1 H NMR (CDCl3, 400 MHz): δ7.38-7.50 (m, 11H), 7.21 (s, 2H in B), 7.19 (s, 2H in A), 6.99 (d, J = 7.8 Hz, 2H in A), 6.96 (d, J = 1.1 Hz, 2H in B), 6.86 (d, J = 7.8 Hz, 2H in B), 6.82 (d, J = 1.1 Hz, 2H in A), 6.09 (s, 2H in B), 1.98-2.04 (m, 18H in B), 1.91- 1.97 (m, 18H in A), 1.74 (m, 12H in B), 1.68-1.74 (m, 12H in A), 1.26 (sept, J=7.6 Hz, 3H in B), 1.23 (sept, J=7.5 Hz, 3H in A), 0.99 (d, J=7.4 Hz, 18H in B), 0.98 (d, J=7.4 Hz, 18H in A), 0.93 (J=7.4 Hz, 18H in B), 0.90 (d, J=7.4 Hz, 18H in A). 13 C NMR (CDCl3, 100 MHz, signals belonging to the minor isomer are marked with *) δ 157.8, 152.8, 152.2*, 140.7*, 139.9, 137.3, 136.9*, 136.7, 136.2*, 135.8*, 135.7, 135.50*, 135.46*, 133.0, 132.0, 131. 6*,130.8*,130.7,129.7,128.9*,128.8,128.4*,128.2*,127.8,124.0*,123.9,122.3,122.2*,40.5,37.11,37.07,36.8*,29.1,18.6,18.59*,18.5,10.74*,10.7.

[0112] (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)(tert-butyl)diphenylsilane To a solution of 1-(5-bromo-2-(methoxymethoxy)phenyl)adamantane (1.48 g, 4.2 mmol) in THF (5 mL) was added dropwise t-BuLi (1.7 M, 5.0 mL, 8.4 mmol) in pentane at -60 ° C over 10 minutes. The reaction mixture was stirred at -60 ° C for 1 hour, and then (tert-butyl)diphenylchlorosilane (1.16 g, 4.2 mmol) was added. The solution was stirred at -60 ° C for 30 minutes, and then stirred at ambient temperature for 1 hour. The reactant was poured into water (10 mL), and the resulting mixture was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The crude product was used in the next step without further purification. 1 H NMR(400MHz, CDCl3) δ7.74(ddd,J=15.5,7.9,1.8Hz,1H),7.61-7.55(m,4H),7.52(d,J=1.8Hz,1H),7.46 -7.31(m,6H),7.03(d,J=8.2Hz,1H),5.24(s,2H),3.53(s,3H),2.06(br,9H),1.75(br,6H),1.17(s,9H).

[0113] (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(tert-butyl)diphenylsilane To a solution of (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)(tert-butyl)diphenylsilane (2.30 g, 4.5 mmol) in diethyl ether (10 mL) was added n-BuLi (1.6 M, 2.8 mL, 4.5 mmol) in hexanes at ambient temperature. The solution was stirred for 1 hour and then concentrated to dryness. The crude solid was slurried in cold pentane (5 mL) for 5 minutes and collected by filtration as a white solid (1.14 g, 43%).

[0114] The lithiated intermediate (1.14 g, 1.9 mmol) was dissolved in hexane. 2-Bromochlorobenzene (0.41 g, 2.1 mmol) in hexane (1 mL) was added dropwise to the resulting solution at 60°C. The reaction was stirred at 60°C for 1 hour and then filtered through Celite. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (10% dichloromethane in hexane) to give the product as a foamy solid (1.20 g, 93%). 1 H NMR (400MHz, CDCl3) δ7.70-7.58(m,5H),7.54(d,J=1.8Hz,1H),7.44-7.32(m,8H),7.31(d,J=1.7Hz,1H),7.19(td,J=7. 7,1.9Hz,1H),4.60(d,J=4.7Hz,1H),4.43(d,J=4.7Hz,1H),3.25(s,3H),2.14-2.04(m,9H),1.77(br,6H),1.19(s,9H).

[0115] (4-(1-adamantyl)-6-isopropoxy-benzo[c][1,2]benzoxaborin-2-yl)(tert-butyl)diphenylsilane To a solution of (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(tert-butyl)diphenylsilane (1.19 g, 1.8 mmol) in THF (5 mL) was added n-BuLi (2.5 M, 0.79 mL, 2.0 mmol) in hexanes at -60°C over 10 minutes. The reaction mixture was stirred at -60°C for 1 hour, then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.50 g, 2.7 mmol) was added. The resulting suspension was stirred at ambient temperature for 1 hour, then poured into 5 mL of water. The resulting mixture was extracted with dichloromethane (2×5 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness.

[0116] Isopropanol (20 mL) was added to the residue and the resulting solution was refluxed for 2 hours. After the reaction was cooled to ambient temperature, the reaction was concentrated. The product slowly precipitated out of solution below -20 °C and was collected by filtration as a white solid (0.85 g, 78%). 1H NMR (400 MHz, CDCl3) δ 8.20 (s, 1H), 8.04 (d, J = 7.5 Hz, 1H), 7.85 (dd, J = 17.6, 8.2 Hz, 1H), 7.66-7.61 (m, 4H), 7.61-7.49 (m, 2H), 7.46-7.31 (m, 7H), 5.35-5.13 (m, 1H in A), 4.03 (td, J = 6.3, 4.1 Hz, 1H in A), 2.25-2.18 (m, 6H), 2.11 (br, 3H), 1.81 (br, 6H), 1.41 (d, J = 6.1 Hz, 3H), 1.26-1.18 (m, 12H).

[0117] 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-((tert-butyl)diphenylsilyl)-[1,1'-biphenyl]-2-phenol) Then, (4-(1-adamantyl)-6-isopropoxy-benzo[c][1,2]benzoxaborin-2-yl)(tert-butyl)diphenylsilane (0.73 g, 1.2 mmol) was added to 1,4-diphenylsilane. To a solution in 2,6-dibromopyridine (0.14 g, 0.60 mmol), potassium carbonate (0.50 g, 3.6 mmol), Buchwald RuPhos Palladacycle Gen I precatalyst (Strem, CAS 1028206-60-1, 4 mg, 0.006 mmol) and water (2 mL) was added. This mixture was stirred at 100 ° C for 16 hours, then cooled to ambient temperature and diluted with water (5 mL). The obtained mixture was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was purified on silica gel by flash chromatography (eluting impurities with 20% dichloromethane in hexane, then eluting the product with 30% dichloromethane + 10% EtOAc in hexane). The isolated product, a mixture of two isomers, was a foamy solid (0.46 g, 66%). 1H NMR (400 MHz, CDCl3) δ 7.52-7.22 (m, 31H), 6.98 (s, 2H), 6.94 (d, J = 7.8 Hz, 2H in A), 6.90 (d, J = 1.6 Hz, 2H in A), 6.82 (d, J = 7.8 Hz, 2H in B), 6.16 (s, 2H in B), 1.96-1.88 (m, 10H), 1.80 (br, 8H), 1.71-1.61 (m, 12H), 1.02 (s, 18H in A), 1.00 (s, 18H in B).

[0118] (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)(tert-butyl)dimethylsilane To a solution of 13.0 g (37.0 mmol) of 1-(5-bromo-2-(methoxymethoxy)phenyl)adamantane in 300 ml of dry THF was added dropwise 42.0 mL (75.8 mmol) of 1.8 M t-BuLi in pentane at -80°C over 30 minutes. The reaction mixture was stirred at this temperature for 1 hour and then 6.69 g (44.4 mmol) of tert-butylchlorodimethylsilane were added. The resulting solution was stirred at room temperature for 1 hour and then poured into 300 mL of water. The obtained mixture was extracted with dichloromethane (3 x 100 mL); the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residue was recrystallized from n-hexane. 11.5 g (80%) of a pale yellow solid were produced. 1 H NMR (CDCl3, 400MHz): δ7.48 (d, J=1.6Hz, 1H), 7.40 (dd, J=8.1, 1.6Hz, 1H), 7.18 (d, J=8.1Hz, 1H), 5.33 (s,2H),3.61(s,3H),2.22-2.27(m,6H),2.18(br.s,3H),1.85-1.93(m,6H),0.98(s,9H),0.36(s,6H). 13 CNMR (CDCl3, 100MHz): δ157.1,137.1,133.4,132.7,129.2,113.5,94.0,56.2,40.7,37.13,37.06,29.1,26.5,16.9,-6.0.

[0119] (3-(1-adamantyl)-4-(methoxymethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)(tert-butyl)dimethylsilane To a solution of 11.5 g (29.7 mmol) of (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)(tert-butyl)dimethylsilane in 300 mL of diethyl ether was added dropwise 17.8 mL (44.6 mmol) of 2.5 M n-BuLi in hexane at 0°C over 20 minutes. The reaction mixture was stirred at room temperature for 12 hours and then cooled to -80°C, followed by the addition of 12.2 mL (59.4 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The obtained mixture was extracted with dichloromethane (3×300 mL); the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residue was recrystallized from n-hexane. 14.1 g (93%) of a white solid were produced. 1 H NMR (CDCl3, 400MHz): δ7.66 (d, J = 1.7Hz, 1H), 7.52 (d, J = 1.7Hz, 1H), 5.23 (s, 2H), 3.60 (s, 3H), 2.14-2.20(m,6H),2.09(br.s,3H),1.77-1.85(m,6H),1.37(s,12H),0.89(s,9H),0.27(s,6H). 13 C NMR (CDCl3, 100MHz): δ162.7,140.7,139.6,136.1,130.5,100.5,83.6,57.7,41.2,37.12,37.05,29.2,26.6,24.8,16.9,-6.0.

[0120] (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(tert-butyl)dimethylsilane Then, 14.0 g (27.4 mmol) of (3-(1-adamantyl)-4-(methoxymethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)(tert-butyl)dimethylsilane was added to 80 mL of 1,4-dioxaborolan-2-yl 8.15 g (28.8 mmol) of 2-bromoiodobenzene, 11.4 g (82.3 mmol) of potassium carbonate and 40 mL of water were added to a solution in oxane. The obtained mixture was purged with argon for 10 minutes, and then 1.57 g (1.36 mmol) of Pd(PPh3)4 was added. This mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 100 ml of water. The obtained mixture was extracted with dichloromethane (3×100 mL); the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane=10:1, volume). 6.75 g (46%) of a white solid was produced. 1 H NMR (CDCl3, 400MHz): δ7.70 (dd, J=8.0, 1.0Hz, 1H), 7.47 (d, J=1.6Hz, 1H), 7.41 (dd, J=7.6, 1.8Hz, 1H), 7.37 (dt, J=7.4, 1.0Hz, 1H), 7.20-7.25 (m, 2H ),4.57-4.58(m,1H),4.44-4.45(m,1H),3.25(s,3H),2.18-2.23(m,6H),2 .13(br.s,3H),1.78-1.86(m,6H),0.90(s,9H),0.30(s,3H),0.28(s,3H). 13 C NMR (CDCl3, 100MHz): δ154.7,141.6,141.3,136.1,133.7,133.0,132.9,132.4,131. 5,128.6,127.1,124.2,98.9,57.2,41.3,37.4,37.0,29.2,26.5,17.0,-6.10,-6.13.

[0121] (4-(1-adamantyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborin-2-yl)(tert-butyl)dimethylsilane To a solution of 6.75 g (12.6 mmol) of (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(tert-butyl)dimethylsilane in 100 mL of dry THF, 5.31 mL (13.3 mmol) of 2.5 M n-BuLi in hexane were added dropwise over 20 minutes at -80°C. The reaction mixture was stirred at this temperature for 1 hour, then 3.83 mL (18.9 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane were added. The obtained suspension was stirred at room temperature for 1 hour, then poured into 300 mL of water. The obtained mixture was extracted with dichloromethane (3×100 mL); the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. 120 mL of isopropanol were added to the residue, and the resulting solution was refluxed for 2 hours. After cooling to room temperature, the precipitate formed was filtered off using a glass frit (G4), washed with 10 mL of cold isopropanol and then dried under vacuum. Yield: 6.14 g (96%) of a white solid. 1 H NMR (CDCl3, 400MHz): δ8.21(s,1H),8.20(d,J=8.0Hz,1H),8.09(dd,J=7.5,1.4Hz,1H),7.67(dt,J=8.2,1.5Hz,1H),7.50(d,J=1.3Hz,1H),7.43(t ,J=7.4Hz,1H),5.27(sept,J=6.2Hz,1H),2.29-2.33(m,6H),2.18(br.s, 3H), 1.83-1.89 (m, 6H), 1.43 (d, J = 6.2Hz, 6H), 0.94 (s, 9H), 0.37 (s, 6H). 13 C NMR (CDCl3, 100MHz): δ151.2,140.7,138.3,133.1,132.4,131.9,129.9,128. 1,126.7,122.2,121.6,65.8,40.8,37.3,37.2,29.1,26.6,24.7,17.0,-5.9.

[0122] 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-phenol) Then, 5.87 g (12.1 mmol) of (4-(1-adamantyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborin-2-yl)(tert-butyl)dimethylsilane was added to 30 mL of 1,4-dihydro-1,4-diol. 1.32 g (5.56 mmol) of 2,6-dibromopyridine, 11.8 g (36.2 mmol) of cesium carbonate and 15 mL of water were added to a solution in oxane. The obtained mixture was purged with argon for 10 minutes, and then 703 mg (0.61 mmol) of Pd(PPh3)4 was added. This mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The obtained mixture was extracted with dichloromethane (3×50 mL); the combined organic extracts were dried over Na2SO4 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, volume). 4.21 g (84%) of a mixture of two isomers was produced as a white powder. 1 H NMR (CDCl3, 400 MHz): δ 8.25 (s, 2H in A), 7.36-7.56 (m, 9H), 7.20 (d, J = 1.3 Hz, 2H in A), 7.03 (d, J = 1.4 Hz, 2H in B), 6.97 (d, J = 7.8 Hz, 2H in A), 6.94 (d, J = 7.8 Hz, 2H in B), 6.72 (d, J = 1.6 Hz, 2H in A). =1.4 Hz, 2H in A), 6.70 (d, J =1.3 Hz, 2H in B), 1.83-2.04 (m, 18H), 1.63-1.72 (m, 12H), 0.75 (s, 18H in B), 0.61 (s, 18H in A), 0.15 (s, 12H in B), 0.05 (s, 6H in A), 0.04 (s, 6H in A). 13 C NMR(CDCl3,100MHz)δ157.7,153.3,139.3,137.3,137.0,135.4,132.2,132.0,131.1 ,129.8,129.0,127.9,127.2,122.6,40.5,37.0,36.8,29.1,26.3,16.7,-6.1,-6.3.

[0123] (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)(butyl)dimethylsilane To a solution of 1-(5-bromo-2-(methoxymethoxy)phenyl)adamantane (2.10 g, 6.0 mmol) in THF (5 mL) was added t-BuLi (1.7 M, 7.0 mL, 12.0 mmol) in pentane at -60°C over 10 minutes. The reaction mixture was stirred at -60°C for 1 hour, then (butyl)dimethylsilyl chloride (0.90 g, 6.0 mmol) was added. The solution was stirred at -60°C for 30 minutes, then stirred at ambient temperature for 1 hour. The reaction was poured into water (10 mL), and the resulting mixture was extracted with dichloromethane (3 x 10 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel (10% dichloromethane in hexanes) to give the product as a foamy solid (1.51 g, 65.3%). 1 H NMR (400MHz, CDCl3) δ7.37(d,J=1.7Hz,1H),7.29(dd,J=8.0,1.6Hz,1H),7.08(d,J=8.0Hz,1H),5.23(s,2H),3.5 2(s,3H),2.26-1.96(m,9H),1.78(br,6H),1.45-1.20(m,4H),0.95-0.81(m,3H),0.77-0.65(m,2H),0.23(s,6H).

[0124] (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(butyl)dimethylsilane To a solution of (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)(butyl)dimethylsilane (1.70 g, 4.4 mmol) in diethyl ether (10 mL) was added n-BuLi (1.6 M, 2.8 mL, 4.4 mmol) in hexanes at ambient temperature. The solution was stirred for 1 hour and then concentrated to dryness. The lithiated intermediate was dissolved in hexanes. To the resulting solution was added 2-bromochlorobenzene (0.88 g, 4.6 mmol) in hexanes (1 mL) dropwise at 60°C. The reaction was stirred at 60°C for 1 hour and then filtered through Celite. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (10% dichloromethane in hexanes) to give the product as a foamy solid (1.94 g, 81%). 1H NMR (400MHz, CDCl3) δ7.68 (dd, J=8.0, 1.2Hz, 1H), 7.45 (d, J=1.7Hz, 1H), 7.40 (dd ,J=7.6,1.9Hz,1H),7.35(td,J=7.4,1.2Hz,1H),7.23-7.20(m,1H),7.19(d,J=1.7 Hz,1H),4.48(dd,J=43.0,4.7Hz,2H),3.23(s,3H),2.28-2.04(m,9H),1.79(br,6H ),1.39-1.28(m,4H),0.93-0.82(m,3H),0.79-0.66(m,2H),0.25(d,J=4.2Hz,6H).

[0125] (4-(1-adamantyl)-6-isopropoxy-benzo[c][1,2]benzoxaborin-2-yl)(butyl)dimethylsilane To a solution of (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(butyl)dimethylsilane (1.94 g, 3.6 mmol) in THF (5 mL) was added n-BuLi (2.5 M, 1.60 mL, 3.9 mmol) in hexanes at -60°C over 10 minutes. The reaction mixture was stirred at -60°C for 1 hour, then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.00 g, 5.4 mmol) was added. The resulting suspension was stirred at ambient temperature for 1 hour, then poured into 5 mL of water. The resulting mixture was extracted with dichloromethane (3×5 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness.

[0126] Isopropanol (20 mL) was added to the residue and the resulting solution was refluxed for 4 hours. After the reaction was cooled to ambient temperature, the reaction was concentrated. Below -20°C, the crude product slowly precipitated out of the solution as a white solid. The pure product (1.32 g, 76%) was isolated by filtration. 1H NMR (400 MHz, CDCl3) δ 8.27-8.15 (m, 2H), 8.06 (d, J = 7.4 Hz, 1H), 7.68 (dddd, J = 22.7, 8.4, 7.2, 1.6 Hz, 1H), 7.52-7.37 (m, 2H), 5.25 (p, J = 6.1 Hz, 1H in A), 4.04 (pd, J = 6.1 ,4.2Hz,1H in A),2.36-2.07(m,9H),1.85(br,6H),1.41(d,J=6.1Hz,3H),1.40-1.31(m,4H),1.22(d,J=6.1Hz,3H),0.94-0.85(m,3H),0.85-0.75(m,2H),0.33(s,6H).

[0127] 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(butyldimethylsilyl)-[1,1'-biphenyl]-2-phenol) To a solution of (4-(1-adamantyl)-6-isopropoxy-benzo[c][1,2]benzoxaborin-2-yl)(butyl)dimethylsilane (1.21 g, 2.50 mmol) in THF (8 mL) was then added 2,6-dibromopyridine (0.29 g, 1.25 mmol), potassium carbonate (1.03 g, 7.5 mmol), Buchwald RuPhos Palladacycle Gen I procatalyst (Strem, CAS1028206-60-1, 9.1 mg, 0.01 mmol,) and water (2 mL). This mixture was stirred at 90° C. for 16 hours, then cooled to ambient temperature and diluted with water (5 mL). The obtained mixture was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel (20% dichloromethane in hexanes to elute the impurities, then 30% dichloromethane in hexanes + 10% EtOAc to elute the product). The product was isolated as a mixture of two isomers as a foamy solid (0.89 g, 78%). 1H NMR (400 MHz, CDCl3) δ 8.13 (s, 2H in A), 7.54-7.34 (m, 9H), 7.21 (s, 2H), 7.09 (d, J = 1.5 Hz, 2H in B), 7.06-6.96 (m, 2H), 6.86 (s, 2H in B), 6.72 (d, J = 1.5 Hz, 2H in A), 2.06-1.75 (m, 18H), 1.73-1.57 (m, 12H), 1.36-1.20 (m, 8H in A), 1.18-1.09 (qd, J = 8.3, 5.8 Hz, 8H in B), 0.84 (t, J = 7.2 Hz, 6H), 0.68-0.59 (m, 4H in B), 0.53 (td, J = 7.8, 5.9 Hz, 4H in A), 0.13 (s, 12H in B), 0.00 (d, J = 6.0 Hz, 12H in A).

[0128] (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)(octyl)dimethylsilane To a solution of 1-(5-bromo-2-(methoxymethoxy)phenyl)adamantane (2.00 g, 5.7 mmol) in THF (5 mL) was added t-BuLi (1.7 M, 6.7 mL, 11.4 mmol) in pentane at -60°C over 10 minutes. The reaction mixture was stirred at -60°C for 1 hour, then dimethyl(octyl)chlorosilane (1.18 g, 5.7 mmol) was added. The solution was stirred at -60°C for 30 minutes, then stirred at ambient temperature for 1 hour. The reactants were poured into water (10 mL), and the resulting mixture was extracted with dichloromethane (2 x 10 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel (10% dichloromethane in hexanes) to give the product as a foamy solid (1.78 g, 71%). 1 H NMR (400MHz, CDCl3) δ7.37(d,J=1.7Hz,1H),7.29(dd,J=8.0,1.6Hz,1H),7.08(d,J=8.0Hz,1H),5.23(s,2H),3.52(s ,3H),2.17-2.03(m,9H),1.83-1.65(m,6H),1.41-1.13(m,12H),0.91-0.86(m,3H),0.77-0.63(m,2H),0.22(s,6H).

[0129] (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(octyl)dimethylsilane To a solution of (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)(octyl)dimethylsilane (1.77 g, 4.0 mmol) in diethyl ether (10 mL) was added n-BuLi (1.6 M, 2.5 mL, 4.0 mmol) in hexanes at ambient temperature. The solution was stirred for 1 hour and then concentrated to dryness. The lithiated intermediate was dissolved in hexanes. To the resulting solution was added 2-bromochlorobenzene (0.84 g, 4.4 mmol) in hexanes (1 mL) dropwise at 60°C. The reaction was stirred at 60°C for 1 hour and then filtered through Celite. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (10% dichloromethane in hexanes) to give the product as a foamy solid (1.74 g, 73%). 1 H NMR (400MHz, CDCl3) δ7.68(d,J=7.9Hz,1H),7.45(s,1H),7.42-7.31(m,2H),7.24-7.14(m,2H),4.60-4.26(m,2H),3.23( s,3H),2.26-2.02(m,9H),1.79(br,6H),1.40-1.22(m,12H),0.93-0.83(m,3H),0.73(t,J=7.9Hz,2H),0.29-0.20(m,6H).

[0130] (4-(1-adamantyl)-6-hydroxy-benzo[c][1,2]benzoxaborin-2-yl)(octyl)dimethylsilane To a solution of (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(octyl)dimethylsilane (1.70 g, 2.8 mmol) in THF (5 mL) was added n-BuLi (2.5 M, 1.25 mL, 3.1 mmol) in hexanes at -60°C over 10 minutes. The reaction mixture was stirred at -60°C for 1 hour, then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.79 g, 4.3 mmol) was added. The resulting suspension was stirred at ambient temperature for 1 hour, then poured into 5 mL of water. The resulting mixture was extracted with dichloromethane (3×5 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness.

[0131] Isopropyl alcohol (20mL) was added to the residue, and the resulting solution was refluxed for 2 hours. After the reaction was cooled to ambient temperature, the reactant was concentrated to dryness. The product was purified on silica gel by flash chromatography (using 20% ​​dichloromethane in hexane to elute impurities, then 20% dichloromethane in hexane + 20% EtOAc to elute the product). The isolated product was a foamy solid (0.90g, 58%). 1 H NMR (400MHz, CDCl3) δ8.36-8.17(m,2H),8.08(dd,J=13.4,7.4Hz,1H),7.73(dt,J=14.8,7.7Hz,1H),7.51-7.38(m,2 H), 4.51 (s, 1H), 2.30-2.06 (m, 9H), 1.87-1.74 (m, 6H), 1.44-1.12 (m, 12H), 0.95-0.68 (m, 5H), 0.33 (d, J = 5.9Hz, 6H).

[0132] 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(octyldimethylsilyl)-[1,1'-biphenyl]-2-phenol) Then, (4-(1-adamantyl)-6-hydroxy-benzo[c][1,2]benzoxaborin-2-yl)(octyl)dimethylsilane (0.85 g, 1.56 mmol) was added to 1,4-dihydro- To a solution in 2,6-dibromopyridine (0.18 g, 0.78 mmol), potassium carbonate (0.65 g, 4.7 mmol), Buchwald RuPhos Palladacycle Gen I precatalyst (Strem, CAS 1028206-60-1, 5.7 mg, 0.008 mmol) and water (2 mL) was added. This mixture was stirred at 100 °C for 16 hours, then cooled to ambient temperature and diluted with water (5 mL). The obtained mixture was extracted with dichloromethane (2 x 10 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was purified on silica gel by flash chromatography (eluting impurities with 25% dichloromethane in hexane, then eluting the product with 30% dichloromethane + 10% EtOAc in hexane). The isolated product, a mixture of two isomers, was a foamy solid (0.46 g, 57%). 1H NMR (400 MHz, CDCl3) δ 8.11 (s, 2H in A), 7.54-7.32 (m, 9H), 7.17 (s, 2H), 7.06 (s, 2H in B), 6.99 (dd, J = 8.1, 4.2 Hz, 2H), 6.84 (s, 2H in B), 6.68 (s, 2H in A), 2.03-1.74 (m, 18H), 1.66 (br, 12H), 1.32-1.18 (m, 24H), 0.87 (t, J = 6.5 Hz, 6H), 0.65-0.38 (m, 4H), 0.00 (s, 12H in B), -0.04 (d, J = 4.9 Hz, 12H in A).

[0133] (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)(3,3-dimethylbutyl)dimethylsilane To a solution of 1-(5-bromo-2-(methoxymethoxy)phenyl)adamantane (2.15 g, 6.1 mmol) in THF (5 mL) was added t-BuLi (1.7 M, 7.2 mL, 12.2 mmol) in pentane at -60°C over 10 minutes. The reaction mixture was stirred at -60°C for 1 hour, then (3,3-dimethylbutyl)-dimethylchlorosilane (1.09 g, 6.1 mmol) was added. The solution was stirred at -60°C for 30 minutes, then stirred at ambient temperature for 1 hour. The reaction was poured into water (10 mL), and the resulting mixture was extracted with dichloromethane (2 x 10 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel (10% dichloromethane in hexanes) to give the product as a foamy solid (1.97 g, 78%). 1 H NMR (400MHz, CDCl3) δ7.37(d,J=1.7Hz,1H),7.30(dd,J=8.0,1.6Hz,1H),7.08(d,J=8.1Hz,1H),5.24(s,2H),3 .52(s,3H),2.23-2.01(m,9H),1.78(br,6H),1.25-1.11(m,2H),0.85(s,9H),0.71-0.56(m,2H),0.22(s,6H).

[0134] (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(3,3-dimethylbutyl)dimethylsilane To a solution of (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)(3,3-dimethylbutyl)-dimethylsilane (1.96 g, 4.7 mmol) in diethyl ether (10 mL) was added n-BuLi (1.6 M, 3.0 mL, 4.7 mmol) in hexanes at ambient temperature. The solution was stirred for 1 hour and then concentrated to dryness. The lithiated intermediate was dissolved in hexanes. To the resulting solution was added 2-bromochlorobenzene (0.95 g, 5.0 mmol) in hexanes (1 mL) dropwise at 60°C. The reaction was stirred at 60°C for 1 hour and then filtered through Celite. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (10% dichloromethane in hexanes) to give the product as a foamy solid (2.45 g, 91%). 1 H NMR (400MHz, CDCl3) δ7.68(dd,J=8.1,1.2Hz,1H),7.45(d,J=1.6Hz,1H),7.42-7.31(m,2H),7.24-7.14(m,2H),4.54(d,J=4.6Hz,1H),4.42 (d,J=4.6Hz,1H),3.23(s,3H),2.28-2.04(m,9H),1.79(br,6H),1.24-1.15(m,2H),0.84(s,9H),0.70-0.59(m,2H),0.24(d,J=6.4Hz,6H).

[0135] (4-(1-adamantyl)-6-isopropoxy-benzo[c][1,2]benzoxaborin-2-yl)(3,3-dimethylbutyl)dimethylsilane To a solution of (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(3,3-dimethylbutyl)dimethylsilane (2.42 g, 4.2 mmol) in THF (5 mL) was added n-BuLi (2.5 M, 1.90 mL, 4.7 mmol) in hexanes at -60°C over 10 minutes. The reaction mixture was stirred at -60°C for 1 hour, then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.19 g, 6.3 mmol) was added. The resulting suspension was stirred at ambient temperature for 1 hour, then poured into 5 mL of water. The resulting mixture was extracted with dichloromethane (3×5 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness.

[0136] Isopropanol (20 mL) was added to the residue and the resulting solution was refluxed for 16 hours. After the reaction was cooled to ambient temperature, the reaction was concentrated and cooled to below -20°C for 1 hour. The product was collected by filtration and washed with a small amount of cold isopropanol to give a white solid (1.54 g, 70%). 1 H NMR (400 MHz, CDCl3) δ 8.27-8.16 (m, 2H), 8.06 (d, J = 7.7 Hz, 1H), 7.68 (dtd, J = 23.3, 8.2, 7.7, 1.5 Hz, 1H), 7.53-7.37 (m, 2H), 5.25 (p, J = 6.2 Hz, 1H in A), 4.03 (p, J = 6.1 Hz, 1H in A), 2.37-2.07 (m, 9H), 1.84 (d, J = 3.3 Hz, 6H), 1.41 (d, J = 6.1 Hz, 3H), 1.27-1.13 (m, 5H), 0.87 (s, 9H), 0.79-0.67 (m, 2H), 0.32 (s, 6H).

[0137] 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-((3,3-dimethylbutyl)dimethylsilyl)-[1,1'-biphenyl]-2-phenol) Then, (4-(1-adamantyl)-6-isopropoxy-benzo[c][1,2]benzoxaborin-2-yl)(3,3-dimethylbutyl)dimethylsilane (1.52 g, 3.0 mmol) was added to 1,4-dimethoxy- 2,6-dibromopyridine (0.35 g, 1.5 mmol), potassium carbonate (1.23 g, 8.9 mmol), Buchwald RuPhos PalladacycleGen I precatalyst (Strem, CAS 1028206-60-1, 11.0 mg, 0.015 mmol) and water (2 mL) were added to a solution in 1,2-dibromopyridine (0.35 g, 1.5 mmol), potassium carbonate (1.23 g, 8.9 mmol), Buchwald RuPhos PalladacycleGen I precatalyst (Strem, CAS 1028206-60-1, 11.0 mg, 0.015 mmol) and water (2 mL). This mixture was stirred at 100°C for 16 hours, then cooled to ambient temperature and diluted with water (5 mL). The obtained mixture was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel (eluting impurities with 10% dichloromethane in hexane and then eluting the product with 20% dichloromethane in hexane). The isolated product, a mixture of two isomers, was a foamy solid (1.29 g, 90%). 1H NMR (400 MHz, CDCl3) δ 8.02 (s, 2H in A), 7.57-7.33 (m, 9H), 7.21-7.15 (m, 2H), 7.08 (d, J = 1.5 Hz, 2H in B), 7.02 (d, J = 7.7 Hz, 2H), 6.85 (s, 2H in B), 6.71 (d, J = 1.5 Hz, 2H in A), 1.9 9-1.84 (m, 18H), 1.74-1.50 (m, 12H), 1.18-1.04 (m, 4H), 0.82 (s, 18H), 0.61-0.52 (m, 4H in B), 0.54-0.40 (m, 4H in A), 0.12 (d, J = 3.9 Hz, 12H in B), -0.03 (d, J = 14.3 Hz, 12H in A).

[0138] (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)(2,4,4-trimethylpentyl)dimethylsilane To a solution of 1-(5-bromo-2-(methoxymethoxy)phenyl)adamantane (2.08 g, 5.9 mmol) in THF (5 mL) was added t-BuLi (1.7 M, 7.0 mL, 12.0 mmol) in pentane at -60°C over 10 minutes. The reaction mixture was stirred at -60°C for 1 hour, then (2,4,4-trimethylpentyl)-dimethylsilyl chloride (1.27 g, 6.1 mmol) was added. The solution was stirred at -60°C for 30 minutes, then stirred at ambient temperature for 1 hour. The reaction was poured into water (10 mL), and the resulting mixture was extracted with dichloromethane (2 x 10 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel (10% dichloromethane in hexanes) to give the product as a foamy solid (1.61 g, 61%). 1 H NMR (400MHz, CDCl3) δ7.37(d,J=1.6Hz,1H),7.29(dd,J=8.1,1.6Hz,1H),7.07(d,J=8.1Hz,1H),5.23(s,2H),3.51(s,3H),2.36-1.97(m,9H),1. 78(br,6H),1.23(dd,J=14.0,4.3Hz,1H),1.11(dd,J=13.9,6.4Hz,1H),1.00-0.78(m,14H),0.69(dd,J=14.7,8.8Hz,1H),0.27(d,J=3.0Hz,6H).

[0139] (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(2,4,4-trimethylpentyl)dimethylsilane To a solution of (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)(2,4,4-trimethylpentyl)dimethylsilane (1.60 g, 3.6 mmol) in diethyl ether (10 mL) was added n-BuLi (1.6 M, 2.3 mL, 3.6 mmol) in hexanes at ambient temperature. The solution was stirred for 1 hour and then concentrated to dryness. The lithiated intermediate was dissolved in hexanes. To the resulting solution was added 2-bromochlorobenzene (0.70 g, 3.6 mmol) in hexanes (1 mL) dropwise at 60°C. The reactants were stirred at 60°C for 1 hour and then filtered through Celite. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (10% dichloromethane in hexanes) to give the product as a foamy solid (1.95 g, 90%). 1 H NMR(400MHz, CDCl3) δ7.68(dd,J=8.0,1.1Hz,1H),7.46(d,J=1.7Hz,1H),7.42-7.31(m,2H),7.24-7.15(m ,2H),4.52(dd,J=4.6,1.4Hz,1H),4.43(d,J=4.7Hz,1H),3.22(s,3H),2.26-2.04(m,9H),1.79(br,6H),1 .21(dt,J=14.0,3.9Hz,1H),1.09(ddd,J=13.9,6.5,3.6Hz,1H),0.97(d,J=6.6Hz,1H),0.91(d,J=6.5Hz, 3H), 0.89-0.82 (m, 1H), 0.81 (d, J = 2.1Hz, 9H), 0.70 (dd, J = 14.7, 8.6Hz, 1H), 0.29 (dd, J = 3.9, 2.7Hz, 6H).

[0140] (4-(1-adamantyl)-6-hydroxy-benzo[c][1,2]benzoxaborin-2-yl)(2,4,4-trimethylpentyl)dimethylsilane To a solution of (5-(1-adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(2,4,4-trimethylpentyl)dimethylsilane (1.95 g, 3.3 mmol) in THF (5 mL) was added dropwise 1% iodine in hexane at -60°C over 10 minutes. nBuLi (2.5M, 1.40mL, 3.6mmol). The reaction mixture was stirred at -60°C for 1 hour, then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.91g, 4.9mmol) was added. The resulting suspension was stirred at ambient temperature for 1 hour, then poured into 5mL of water. The resulting mixture was extracted with dichloromethane (3×5mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness.

[0141] Isopropyl alcohol (20mL) was added to the residue, and the resulting solution was refluxed for 6 hours. After the reaction was cooled to ambient temperature, the reactant was concentrated to dryness. The product was purified on silica gel by flash chromatography (using 20% ​​dichloromethane in hexane to elute impurities, then 20% dichloromethane in hexane + 10% EtOAc to elute the product). The isolated product was a foamy solid (0.53 g, 33%). 1 H NMR(400MHz, CDCl3)δ8.41-8.19(m,2H),8.12(ddd,J=17.0,7.5,1.5Hz,1H),7.80-7.7 0(m,1H),7.56-7.37(m,2H),4.74(s,1H),2.30(d,J=2.9Hz,4H),2.20-2.08(m,5H),1. 95-1.70(m,6H),1.31-1.27(m,1H),1.18(ddd,J=13.9,6.4,2.9Hz,1H),1.00(d,J=6.6 Hz, 1H), 0.96 (dd, J=6.6, 2.8Hz, 3H), 0.94-0.74 (m, 11H), 0.41 (dd, J=6.1, 5.1Hz, 6H).

[0142] 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-((2,4,4-trimethylpentyl)dimethylsilyl)-[1,1'-biphenyl]-2-phenol) Then, (4-(1-adamantyl)-6-hydroxy-benzo[c][1,2]benzoxaborin-2-yl)(2,4,4-trimethylpentyl)dimethylsilane (0.51 g, 1.0 mmol) was added to 1,4-dihydro- To a solution in 2,6-dibromopyridine (0.12 g, 0.5 mmol), potassium carbonate (0.42 g, 3.0 mmol), Buchwald RuPhos Palladacycle Gen I precatalyst (Strem, CAS 1028206-60-1, 3.7 mg, 0.005 mmol) and water (2 mL) was added. This mixture was stirred at 100 °C for 16 hours, then cooled to ambient temperature and diluted with water (5 mL). The obtained mixture was extracted with dichloromethane (2 x 10 mL). The combined organic extracts were dried over MgSO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel (eluting impurities with 10% dichloromethane in hexane and then eluting the product with 20% dichloromethane in hexane). The isolated product, a mixture of two isomers, was a foamy solid (0.45 g, 90%). 1 H NMR (400 MHz, CDCl3) δ 7.97 (dd, J = 84.0, 77.0 Hz, 2H in A), 7.58-7.32 (m, 9H), 7.21 (s, 2H), 7.14-7.07 (m, 2H in B), 7.08-6.98 (m, 2H), 6.89 (dd, J = 35.9, 6.4 Hz, 2H in B), 6.78-6.67 (m, 2H in A), 2.05-1.87 (m, 18H), 1.77-1.57 (m, 12H), 1.26-1.15 (m, 2H), 1.15-1.01 (m, 2H), 0.96-0.70 (m, 28H), 0.66-0.44 (m, 2H), 0.22-0.16 (m, 12H in B), 0.12-0 (m, 12H in A). Preparation of transition metal complexes

[0143] Complex 3 To a suspension of 97 mg (0.301 mmol) of hafnium tetrachloride in 20 mL of dry toluene at 0°C, 436 uL (1.26 mmol) of 2.9 M MeMgBr in diethyl ether was added in one portion via syringe. To the resulting suspension was immediately added in one portion 250 mg (0.301 mmol) of 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(trimethylsilyl)-[1,1'-biphenyl]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The solid obtained was extracted with 2 x 20 mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane; the resulting precipitate was filtered off, washed twice with 5 mL of n-hexane and then dried in vacuo. 266 mg (85%) of a white beige solid was produced. 57 H 69 Calculated values ​​for HfNSi2O2: C, 66.16; H, 6.72; N, 1.35. Found: C 66.47; H, 6.99; N 1.20. 1 H NMR (C6D6, 400MHz): δ7.75 (d, J = 1.7Hz, 2H), 7.28 (d, J = 1.7Hz, 2H), 6.95-7.19 (m, 8H), 6.32-6.39 (m, 3H), 2.51-2. 58(m,6H),2.37-2.44(m,6H),2.18(br.s,6H),1.95-2.02(m,6H),1.80-1.87(m,6H),0.30(s,18H),-0.11(s,6H). 13 C NMR(C6D6,100MHz)δ162.9,157.8,143.5,139.8,138.8,134.4,133.9,133.6,132. 9,132.5,131.7,131.4,128.5,128.3,125.0,51.8,41.9,38.3,37.8,30.0,-0.11.

[0144] Complex 4 To a mixture of ZrCl4(Et2O)2 (63 mg, 0.165 mmol) and 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(triethylsilyl)-[1,1'-biphenyl]-2-phenol) (375 mg, 0.150 mmol) in toluene (-8 mL) cooled at 0°C was added MeMgBr (3.0 M, 0.24 mL, 0.721 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 90 min and heated at -40 ℃ and stored overnight, then evaporated to near dryness. The resulting solid was extracted with pentane (~9mL) and toluene (~1mL). The extract was filtered through diatomaceous earth (Celite) on a glass fiber plug. The resulting filtrate was concentrated under vacuum to an oily residue, which was ground with pentane several times to finally obtain a light brown foam (127mg). The foam was dissolved in pentane and a minimum amount of toluene. The resulting solution was stored at -40 ℃ to obtain colorless crystals, which were isolated by decantation and dried under vacuum. Produced 65.2mg (42%). 1 H NMR (C6D6, 400MHz): δ7.73 (s, 2H), 7.21 (d, J = 8.7Hz, 4H), 7.06 (dt, J = 18.9, 7.4H z,4H),6.92(d,J=7.3Hz,2H),6.55-6.50(m,1H),6.42(d,J=7.6Hz,2H),2.58(d, J=12.1Hz,6H),2.44(d,J=12.3Hz,6H),2.18(s,6H),1.98(d,J=12.0Hz,6H),1.8 3(d,J=12.2Hz,6H),1.05(t,J=7.8Hz,18H),0.83(q,J=7.6Hz,12H),0.14(s,6H).

[0145] Complex 5 To a mixture of ZrCl4(Et2O)2 (82.2 mg, 0.216 mmol) and 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tripropylsilyl)-[1,1'-biphenyl]-2-phenol) (202 mg, 0.203 mmol) in toluene (~3 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.30 mL, 0.900 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 80 minutes and then evaporated to dryness. The resulting solid was extracted with pentane and the combined extracts were filtered through Celite. The filtrate (~10 mL) was stored at ambient temperature and allowed to evaporate slowly. After a few days, the pentane was evaporated to give a clear mass coated with a brown residue, which was washed with cold pentane and then dried in vacuo to give the product as an off-white mass (130.2 mg, 58%).

[0146] Complex 6 To a mixture of ZrCl4(Et2O)2 (143 mg, 0.375 mmol) and 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tributylsilyl)-[1,1'-biphenyl]-2-phenol) (375 mg, 0.347 mmol) in toluene (~6 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.52 mL, 1.56 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 25 minutes and then evaporated to near dryness. The resulting residue was triturated with pentane. The product was ground three times and then concentrated under vacuum to a beige solid. The solid was extracted with pentane and the combined extracts were filtered through diatomaceous earth (Celite). The filtrate (already containing some microcrystalline material) was then stored at -40 ° C and allowed to evaporate slowly. After a few days, the brown supernatant was removed and the remaining solid was washed with cold pentane (3 × 0.5 mL) and then vacuum dried to obtain the product as a white microcrystalline solid (136 mg, 33%). The supernatant and pentane washings were combined and concentrated under vacuum to a brown foam (223 mg). Total mass recovery: 359 mg, 86%. 1H NMR (C6D6, 400MHz): δ7.78 (d, J=1.8Hz, 2H), 7.32-7.21 (m, 4H), 7.07 (dtd, J=21.1, 7.4, 1.5Hz, 4H), 6.95 (dd, J=7.5, 1.6Hz, 2H), 6.75-6.67 (m, 1 H),6.50(d,J=7.8Hz,2H),2.68-2.39(m,12H),2.17(d,J=5.1Hz,6H),2. 04-1.73(m,12H),1.56-1.31(m,24H),1.10-0.70(m,30H),0.14(s,6H).

[0147] Complex 7 To a suspension of 701 mg (3.01 mmol) zirconium tetrachloride in 350 mL dry toluene at -30 °C, 4.36 mL (12.6 mmol, 2.9 M) MeMgBr in diethyl ether was added via syringe in one portion. To the resulting suspension were immediately added 3.00 g (3.01 mmol) of 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(triisopropylsilyl)-[1,1'-biphenyl]-2-phenol) in one portion. The reaction mixture was stirred at room temperature for 3 hours and then evaporated to near dryness. The solid obtained was extracted with 2 x 100 mL of toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 10 mL of n-hexane; the precipitate obtained was filtered off, washed twice with 10 mL of n-hexane and then dried in vacuo. This yielded 3.24 g (96%) of a light beige solid. C 69 H 93 Calculated for ZrSi2NO2: C, 74.27; H, 8.40; N, 1.26. Found: C 74.41; H, 8.58; N 1.10. 1H NMR(C6D6,400MHz): δ7.69(d,J=1.5Hz,2H),7.23(dd,J=7.6,1.2Hz,2H),6.99-7.14( m,6H),6.94(dd,J=7.5,1.3Hz,2H),6.71(t,J=7.7Hz,1H),6.54(d,J=7.8Hz,2H),2.5 4-2.63(m,6H),2.40-2.49(m,6H),2.18(br.s,6H),1.94-2.03(m,6H),1.77-1.86(m, 6H),1.29-1.44(m,6H),1.16(d,J=8.0Hz,24H),1.14(d,J=7.7Hz,12H),0.15(s,6H). 13 C NMR(C6D6,100MHz): δ162.1,158.5,143.6,137.9,136.3,134.6,133.6,133.4 ,133.1,131.7,131.1,124.5,122.3,43.7,42.2,38.4,37.8,30.0,19.3,11.6.

[0148] Complex 8 To a mixture of ZrCl4(Et2O)2 (33.5 mg, 0.088 mmol) and 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-((tert-butyl)diphenylsilyl)-[1,1'-biphenyl]-2-phenol) (96.6 mg, 0.083 mmol) in toluene (~2 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.12 mL, 0.360 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 95 minutes and then evaporated to dryness. The solid was extracted with toluene and the combined extracts were filtered through Celite. The filtrate was concentrated in vacuo to give the product as a solid.

[0149] Complex 9 To a suspension of 766 mg (3.28 mmol) zirconium tetrachloride in 350 mL dry toluene at -30 °C was added 4.80 mL (13.8 mmol) 2.9 M MeMgBr in diethyl ether in one portion via syringe. 3.00 g (3.28 mmol) of 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-phenol were immediately added to the resulting suspension in one portion. The reaction mixture was stirred at room temperature for 3 hours and then evaporated to near dryness. The solid obtained was extracted with 2 x 100 mL of toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 10 mL of n-hexane; the precipitate obtained was filtered off, washed twice with 10 mL of n-hexane and then dried in vacuo. 3.14 g (93%) of a light beige solid were obtained. C 63 Calculated values ​​for H81ZrSi2NO2: C, 73.34; H, 7.91; N, 1.36. Found: C 73.25; H, 7.98; N 1.32. 1 H NMR(C6D6,400MHz): δ7.72(d,J=1.6Hz,2H),7.21-7.24(m,4H),6.99-7.10(m ,4H),6.96(dd,J=7.5,1.8Hz,2H),6.52(dd,J=8.3,7.2Hz,1H),6.39(d,J=7.6 Hz,2H),2.53-2.62(m,6H),2.39-2.48(m,6H),2.17(br.s,6H),1.93-2.02(m, 6H),1.78-1.87(m,6H),0.99(s,18H),0.29(s,6H),0.27(s,6H),0.13(s,6H). 13 C NMR(C6D6,100MHz): δ162.3,158.3,143.5,139.6,137.9,135.4,133.9,133.6,133. 0,131.7,131.2,125.8,124.5,43.7,42.1,38.4,37.8,30.0,27.3,17.7,-5.3,-5.5.

[0150] Complex 10 To a mixture of ZrCl4(Et2O)2 (80 mg, 0.210 mmol) and 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(n-butyldimethylsilyl)-[1,1'-biphenyl]-2-phenol) (180 mg, 0.197 mmol) in toluene (~3 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.30 mL, 0.900 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 80 minutes and then evaporated to near dryness. The resulting solid was extracted with pentane and the combined extracts were filtered through Celite. The filtrate (~2 mL) was stored at ambient temperature and allowed to evaporate slowly. After a few days, the pentane was evaporated to give a solid, which was washed with cold pentane on a plastic fritted funnel and then dried in vacuo to give the product as an off-white powder (75.8 mg, 37%).

[0151] Complex 11 To a mixture of ZrCl4(Et2O)2 (55 mg, 0.144 mmol) and 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(dimethyl(octyl)silyl)-[1,1'-biphenyl]-2-phenol) (141 mg, 0.137 mmol) in toluene (~3 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.2 mL, 0.600 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 30 minutes and then evaporated to near dryness. The resulting solid was extracted with pentane. The extract was filtered through Celite on a glass fiber plug. The resulting filtrate was concentrated in vacuo to give a light brown foam. Yield 54.2 mg (34.5%).

[0152] Complex 12 To a mixture of ZrCl4(Et2O)2 (54.4 mg, 0.143 mmol) and 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-((3,3-dimethylbutyl)dimethylsilyl)-[1,1'-biphenyl]-2-phenol) (130 mg, 0.134 mmol) in toluene (~2 mL) cooled at -40 °C was added MeMgBr (3.0 M, 0.20 mL, 0.600 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 2 hours and then evaporated to dryness. The resulting solid was extracted with pentane and the combined extracts were filtered through Celite.

[0153] Complex 13 To a mixture of ZrCl4(Et2O)2 (55.4 mg, 0.145 mmol) and 2',2"'-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-((2,4,4-trimethylpentyl)dimethylsilyl)-[1,1'-biphenyl]-2-phenol) (140 mg, 0.137 mmol) in toluene (~2 mL) cooled at -40 °C was added MeMgBr (3.0 M, 0.20 mL, 0.600 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 2 hours and then evaporated to dryness. The resulting solid was extracted with pentane and the combined extracts were filtered through Celite. Complex solubility

[0154] General considerations: Solubility studies of complexes 2, 6 and 9 were performed using recrystallized material. Solubility studies of all other complexes were performed using material as synthesized. Complex 2 was co-crystallized with 1.4 equivalents of methylcyclohexane. Complex 9 was co-crystallized with 0.52 equivalents of isohexane. Solvents used were sparged with nitrogen (30-60 minutes) and Dry over molecular sieves. Unless otherwise stated, all measurements were performed at ambient temperature (20-25°C).

[0155] General Procedure: Solubility was determined using either Method 1 or Method 2 below. For calculations, the density of isohexane was used with a value of 0.672 g / mL.

[0156] Method 1. A small amount of complex (actual mass recorded, including any residual solvent as described above, is typically 5-30 mg) is loaded into a tared vial. Then, a small stirring bar (8 mm) is added. Then the solvent is added and the mixture is stirred rapidly (1000 rpm). If a homogeneous mixture is not formed within 30 minutes, additional solvent is added and the mixture is stirred for another 30 minutes. This process is repeated until a clear solution is obtained (no visible solids or turbidity) or the vial is full. When the mixture approaches homogeneity (i.e., very little residual solid is observed), the volume of solvent addition is kept small (<1 mL) to minimize the excess of solvent required to reach homogeneity. Then the stirring bar is removed and the mass of the mixture is measured. If a clear solution is formed, the solubility of the complex is calculated as a single value based on the mass of the complex and the amount of solvent added to obtain a homogeneous solution. If the mixture remains heterogeneous (visible solids or turbidity), the reported value is given as "less than" the calculated value.

[0157] Method 2. A measured amount of the complex (actual mass recorded, including any residual solvent as described above) 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 addition of isohexane. If a clear solution had formed, the solubility was reported as a range, with the lower limit of the solubility calculated using the total solvent added to obtain a homogeneous solution and the upper limit of the solubility calculated using the total solvent measured before a homogeneous solution was obtained. If the mixture remained heterogeneous (visible solids or turbidity), the upper limit of the solubility was calculated using the total solvent added.

[0158] The formula used to calculate solubility is shown below. The solvent present in the complex is included in the mass and molecular weight of the complex (formula weight).

[0159] Solubility (mM) = [10 6 ]×[(grams of complex) / (molecular weight of complex, g / mol)] / [total volume of solvent, mL)], or Solubility (mM) = [10 6 ]×[(grams of complex) / (molecular weight of complex, g / mol)] / [(grams of solvent) / (density of solvent, g / mL)] Solubility (wt%) =

[100] × [(grams of complex) / [(grams of complex) + (total volume of solvent, mL) × (density of solvent, g / mL)]], or Solubility (weight %) =

[100] x [(weight of complex) / (weight of solution)]. Table 1. Solubility of selected complexes in isohexane at ambient temperature. Polymerization Example

[0160] Solutions of the procatalyst were prepared using toluene (ExxonMobil Chemical - anhydrous, stored under N2) (98%) or isohexane (ExxonMobil Chemical - polymerisation grade and purified as described below). Procatalyst solutions were typically 0.5 mmol / L.

[0161] Solvents, polymer-grade toluene and / or isohexane, were supplied by ExxonMobil Chemical Co. and purified by passing through a series of columns: two 500 cc OxyClear cartridges in series from Labclear (Oakland, California), followed by a 100 mL column filled with dry Molecular sieves (8-12 mesh; Aldrich Chemical Company) and two 500 cc columns in series, and Two 500 cc columns of molecular sieves (8-12 mesh; Aldrich Chemical Company) were connected in series.

[0162] Polymer grade propylene (C3) was used and further purified by passing it through a series of columns: a 2250cc Oxyclear cartridge from Labclear followed by A 2250 cc column was filled with molecular sieves (8-12 mesh; Aldrich Chemical Company) and then Molecular sieves (8-12 mesh; Aldrich Chemical Company) were used in two 500 cc columns connected in series, followed by a 500 cc column filled with Selexsorb CD (BASF), and finally a 500 cc column filled with Selexsorb COS (BASF).

[0163] The procatalyst was activated by 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. The activator was typically used as a 0.25 mmol / L solution in toluene or isohexane.

[0164] Tri-n-octylaluminum (TnOAl or TNOA, neat, AkzoNobel) was also used as a scavenger before the activator and procatalyst were introduced into the reactor. TNOA was typically used as a 5 mmol / L solution in toluene or isohexane. Reactor Description and Preparation:

[0165] The polymerization was carried out in an inert atmosphere (N2) dry box using an autoclave equipped with an external heater for temperature control, a glass insert (internal volume of 22.5 mL), a septum inlet, a regulated supply of nitrogen and propylene, and a disposable PEEK mechanical stirrer (800 RPM). 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. Propylene Polymerization (PP):

[0166] The reactor is prepared as described above, then heated to 40°C and then purged with propylene gas at atmospheric pressure. Toluene or isohexane, liquid propylene (1.0 mL) and scavenger (TNOA, 0.5 μmol) are added via a syringe. The reactor is then brought to process temperature (70°C or 100°C) while stirring at 800RPM. The activator solution, followed by the precatalyst solution, is injected into the reactor under process conditions via a syringe. The reactor temperature is monitored and typically maintained within + / -1°C. The polymerization is stopped by adding a mixture of about 50 psi compressed dry air gas to the autoclave for about 30 seconds. The polymerization is quenched based on a predetermined pressure loss (maximum quenching value) or up to 30 minutes. The reactor is cooled and vented. The polymer is isolated after removing the solvent in a vacuum. The actual quenching time (s) is reported as the quenching time (s). The reported yield includes the total weight of the polymer and the residual catalyst. The catalyst activity is reported as grams of polymer / mmol transition metal compound / hour reaction time (g / mmol·hr). Propylene homopolymerization examples are reported in Table 2 and additional characterizations are reported in Table 3. Polymer characterization

[0167] For analytical testing, polymer sample solutions were prepared by dissolving the polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity, obtained from Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%, obtained from Aldrich) at 165°C in a shaker oven for approximately 3 hours. The typical concentration of polymer in solution was 0.1-0.9 mg / mL and the BHT concentration was 1.25 mg BHT / mL TCB. The samples were cooled to 135°C for testing.

[0168] High temperature size exclusion chromatography was performed using an automated "Rapid 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 weight (weight average molecular weight (Mw), number average molecular weight (Mn)) and z-average molecular weight (Mz)) and molecular weight distribution (MWD = Mw / Mn), which is sometimes also referred to as the polydispersity (PDI) of the polymer, are measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD) and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 5000 and 3,390,000). Alternatively, the samples are measured using a Symyx Technology GPC equipped with a dual wavelength infrared detector and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 580 and 3,039,000). Samples 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 (135°C sample temperature, 165°C oven / column) (250 μl of polymer in TCB solution was injected into the system). Column normal time difference correction was not used. A 10 μm HPLC-MS / MS column available from Symyx Technologies was used. Numerical analysis was performed using the Automation Studio software available from Freeslate or the Automation Studio software available from Freeslate. The molecular weights obtained are relative to linear polystyrene standards. The molecular weight data are reported in Table 2 under the headings Mn, Mw, Mz and PDI as defined above.

[0169] 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 allowed to cool to 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 stage. The results are reported in Table 2 under the heading Tm (°C).

[0170] 13 C NMR spectroscopy was used to characterize some of the polypropylene polymer samples prepared in the experiments collected in Table 2. This data is collected in Table 3. Unless otherwise stated, the data used for13 C NMR spectroscopy of polymer samples dissolved in d2-1,1,2,2-tetrachloroethane and heated at 125 °C using 13 The samples were recorded on an NMR spectrometer with a C NMR frequency of 150 MHz. The polymer resonance peak reference mmmm = 21.8 ppm. The calculations involved in the characterization of polymers by NMR followed the works of FA Bovey, "Polymer Conformation and Configuration", Academic Press, New York 1969 and J. Randall, "Polymer Sequence Determination, Carbon-13 NMR Method", Academic Press, New York, 1977.

[0171] The stereo defects measured as "stereo defects / 10,000 monomer units" are calculated by multiplying the sum of the intensities of the mmrr, mmrm+rrmr and rmrm resonance peaks by 5000. The intensity used in the calculation is normalized to the total number of monomers in the sample. The method for measuring 2,1-regio defects / 10,000 monomers and 1,3-regio defects / 10,000 monomers follows 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. Average meso run length = 10000 / [(stereo defect / 10000C)+(2,1-region defect / 10000C)+(1,3-region defect / 10000C)].

[0172] The polymerization results are collected in Tables 2 and 3. "Ex#" represents the example number. Example numbers starting with "C" are comparative examples. "Cat ID" identifies the procatalyst used in the experiment. The corresponding number identifying the procatalyst (also called procatalyst, catalyst, complex or compound) is located in the synthetic experimental section. T (℃) is the polymerization temperature typically maintained within + / -1℃. "Yield" is the polymer yield and is not corrected for catalyst residues. "Quenching Time (s)" is the actual duration of the polymerization run in seconds. For propylene homopolymerization runs, the quenching value represents the maximum set pressure loss (conversion) of propylene (for PP runs) during polymerization. Activity is reported in grams of polymer / mmol catalyst / hour.

[0173] Standard polymerization conditions included 0.015 μmol catalyst complex, 1.1 equivalents activator, 0.5 μmol TNOA scavenger, 1.0 ml propylene, 4.1 ml total solvent, quench value at 8 psi pressure loss, or a maximum reaction time of 30 minutes. 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 procatalyst and activator solutions were in toluene. When activator B was used, both the procatalyst and activator solutions were in isohexane. A small amount of methylcyclohexane (MCH) was generated by activator B, which was provided by the manufacturer as a 10 wt % solution in methylcyclohexane.

[0174] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It is understood that ranges including combinations of any two values, such as any lower limit value combined with any upper limit value, any combination of any two lower limits, and / or any combination of any two upper limits are contemplated unless otherwise stated. Certain lower limits, upper limits, and ranges appear in one or more claims below. All numerical values ​​are "about" or "approximately" indicative values, and take into account experimental errors and deviations that would be expected by a person of ordinary skill in the art. Any value in the table may provide an endpoint defining a range of its corresponding measurement or property, with an additional + / - 10%.

[0175] All documents described herein, including any priority documents and / or test procedures are incorporated by reference in all jurisdictions not inconsistent with the present invention. It is apparent from the above overview and specific embodiments that, although the form of the present disclosure has been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Therefore, it is not desired that the present disclosure be limited in this manner.

[0176] While the present disclosure has been described in terms of a number of embodiments and examples, those skilled in the art, after reading this disclosure, will appreciate that other embodiments can be devised without departing from the scope and spirit of the present disclosure.

Claims

1. A catalyst compound represented by formula (I): in: M is a Group 3, 4 or 5 metal; L is a Lewis base; X is an anionic ligand; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or 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 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 9 , R 10 , R 11 and R 12 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 9 and R 10 , R 10 and R 11 or R 11 and R 12 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 13 , R 14 , R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 13 and R 14 , R 14 and R 15 or R 15 and R 16 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 120 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 or R 17 and R 19 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; Any two L groups can be linked together to form a bidentate Lewis base; The X group can be linked to the L group to form a monoanionic bidentate group; Any two X groups can be linked together to form a dianionic ligand group; and the condition is R 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 At least one of them independently contains A(R a )(R b )(R c ) in the form of a silyl or germanyl group, wherein A is Si or Ge, and R a , R b and R c Each of C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon group, or R a and R b , R a and R c or R b and R c One or more pairs of may be linked to form one or more substituted hydrocarbyl rings or unsubstituted hydrocarbyl rings.

2. The catalyst compound of claim 1, wherein the catalyst compound is represented by formula (II), in: Each of A' and A" is independently Si or Ge; and R a , R b , R c , R d , R e and R f Each of C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon group, or R a and R b , R a and R c , R b and R c , R d and R e , R d and R f or R e and R f One or more pairs of may be linked to form one or more substituted hydrocarbyl rings or unsubstituted hydrocarbyl rings.

3. The catalyst compound of claim 1, wherein R 2 and R 7 Independently containing A(R a )(R b )(R c ) in the form of silyl or germanyl, preferably silyl, wherein A is Si or Ge, preferably Si, and optionally A(R a )(R b )(R c ) contains at least seven carbons.

4. The catalyst compound of claim 1, wherein R 2 and R 7 Each contains A(R a )(R b )(R c ) in the form of a silyl group, wherein A is Si, A(R a )(R b )(R c ) contains at least seven carbon atoms, and R a , R b and R c At least one, preferably two, of the 40 )alkyl or (C2-C 40 ) heteroalkyl containing a linear carbon chain of at least three, preferably four carbons in length bonded to A at the end.

5. The catalyst compound of claim 2, wherein A' and A" are Si, A'(R a )(R b )(R c ) contains at least seven carbons, and A”(R e )(R f )(R g ) contains at least seven carbons.

6. The catalyst compound of claim 2, wherein A' and A" are Si, A'(R a )(R b )(R c ) contains at least seven carbon atoms, R a , R b and R c At least one, preferably two, of the 40 )alkyl or (C2-C 40 ) heteroalkyl, which contains a linear carbon chain of at least three carbons in length bonded to A', A" (R e )(R f )(R g ) contains at least seven carbon atoms, and R d , R e and R f At least one of them is aliphatic (C3-C 40 )alkyl or (C2-C 40 ) heteroalkyl containing a linear carbon chain of at least three, preferably four carbons in length bonded to A" at the end.

7. A catalyst compound according to any of the preceding claims, wherein R 4 and R 5 and are independently adamantyl or substituted adamantyl.

8. The catalyst compound of claim 1, wherein the catalyst compound is one of the following:

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

10. A homogeneous solution comprising: an aliphatic hydrocarbon solvent; and At least one catalyst compound of claim 1 or claim 2, wherein the concentration of the at least one catalyst compound is 0.20 wt % or greater (or 0.25 wt % or greater, or 0.30 wt % or greater, or 0.35 wt % or greater, or 0.40 wt % or greater, or 0.50 wt % or greater, or 1.0 wt % or greater, or 2.0 wt % or greater).

11. The homogeneous solution of claim 10, wherein the aliphatic hydrocarbon solvent is isohexane, cyclohexane, methylcyclohexane, pentane, isopentane, heptane, an isoparaffin solvent, a non-aromatic cyclic solvent, or a combination thereof.

12. A process for producing a propylene-based or ethylene-based polymer or copolymer, comprising: Propylene and / or ethylene and optional comonomers are polymerized by contacting propylene and / or ethylene and optional comonomers with the catalyst system of claim 9 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 the propylene-based or ethylene-based polymer or copolymer.

13. The process of claim 12, wherein the catalyst system and the activator are fed separately into the one or more reactors.

14. The process of claim 12, wherein the catalyst system and the activator are premixed prior to feeding into the one or more reactors.

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