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

Abstract

The present disclosure relates to bis (aryl phenolate) Lewis base transition metal complexes, catalyst systems comprising bis (aryl phenolate) Lewis base transition metal complexes, and polymerization processes to produce polyolefin polymers, such as polyethylene-based polymers and polypropylene-based polymers.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 338,167, 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, it is often challenging to replace aromatic solvents with non-aromatic solvents such as isohexane 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; US 2020 / 0255556; US 2020 / 0255555; US 2020 / 0254431; and US 2020 / 0255553, the entire contents of each of which are hereby incorporated by reference. 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 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R4 , 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 40 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 40 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 40 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 are optionally linked together to form a bidentate Lewis base; The X group is optionally linked to the L group to form a monoanionic bidentate group; and Any two X groups are optionally linked together to form a dianionic ligand group, provided that R 17 , R 18 and R 19 At least one of the moieties contains at least two or more saturated or unsaturated carbon atoms.

[0009] A homogeneous solution comprising: an aliphatic hydrocarbon solvent; and at least one complex of formula (I), wherein the concentration of the complex 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).

[0010] A method for producing a propylene-based polymer, comprising: polymerizing propylene by contacting propylene with a catalyst system prepared by formula (I) in one or more continuous stirred tank reactors or loop reactors connected in series or in 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.

[0011] A method for producing an ethylene-based polymer, comprising: polymerizing ethylene by contacting ethylene with a catalyst system prepared by formula (I) in one or more continuous stirred tank reactors or loop reactors connected in series or in 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 an ethylene-based polymer. DETAILED DESCRIPTION OF THE INVENTION

[0012] 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.

[0013] 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.

[0014] 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 second, h is hour, psi is pounds per square inch, psig is pounds per square inch, gauge pressure, equiv is equivalent, and RPM is revolutions per minute.

[0015] 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.

[0016] The terms "substituent," "radical," "group," and "moiety" are used interchangeably.

[0017] "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.

[0018] "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 ).

[0019] 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).

[0020] 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, 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.

[0021] The term "substituted hydrocarbyl" refers to a hydrocarbyl group wherein at least one hydrogen atom 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 following 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.

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

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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, trihexylsilyl, butyldimethylsilyl, butyldimethylgermyl, dimethyloctylsilyl, dimethyloctylgermyl, etc.

[0029] The terms dihydrocarbylamino and dihydrocarbylphosphino refer to nitrogen or phosphorus groups bonded to two hydrocarbyl groups, which may be optionally linked. Examples of suitable dihydrocarbylamino and dihydrocarbylphosphino groups may include dimethylamino, dimethylphosphino, diethylamino, N-pyrrolidinyl, diethylphosphino, and all isomers of dipropylamino, dipropylphosphino, dibutylamino, dibutylphosphino, etc.

[0030] 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.

[0031] 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. 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.

[0032] The term "thiolate" refers to an alkyl or aryl group bonded to a sulfur atom, such as an alkyl thioether or aryl thioether group containing a sulfur atom, and may include alkyl thioethers or aryl thioethers wherein the alkyl thioether group is C1 to C 10 The alkyl group may be a thiol group, ...

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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 can be C1-C 100 A 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.

[0039] The terms "adamantyl" and "adamantanyl" may be used interchangeably.

[0040] Unless otherwise stated, "C m -C y "C2-C 40 Examples of "substituted hydrocarbyl" can include a C1 hydrocarbyl further substituted with one or more heteroatom-containing groups containing additional carbon (e.g., -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3) such that the resulting substituted hydrocarbyl moiety includes a total of 2 to 40 carbon atoms.

[0041] 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.

[0042] 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.

[0043] Unless otherwise indicated, all melting points (Tm) are differential scanning calorimetry (DSC) second melts.

[0044] 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.

[0045] 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.

[0046] "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.

[0047] 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

[0048] 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 40 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 8One 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 40 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 40 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 40 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 are optionally linked together to form a bidentate Lewis base; The X group is optionally linked to the L group to form a monoanionic bidentate group; and Any two X groups are optionally linked together to form a dianionic ligand group, The condition is R 17 , R 18 and R 19 At least one of the moieties contains at least two or more saturated or unsaturated carbon atoms.

[0049] For example, M of formula (I) 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.

[0050] Each L of formula (I) 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, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamido, diethylamido, dipropylamido and diisopropylamido. In at least one embodiment, n of formula (I) is 2 and each X is independently chloro, benzyl or methyl.

[0051] 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 40 substituted hydrocarbyl, hydrocarbyloxy, trihydrocarbylsilyl, trihydrocarbylgermyl, dihydrocarbylamino, dihydrocarbylphosphino or halogen, 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 R7 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.

[0052] For example, R of formula (I) 4 and R 5 Can be C1-C independently 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 5 is 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 a heteroatom, 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 30The alkyl group (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl, cyclopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., 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 the aryl group is C6 to C 30 Aryl (e.g., phenyl, benzyl, and naphthyl). Typically, R 4 and R 5 It may be triethylsilyl.

[0053] In some embodiments, R 4 and R 5 Each of C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon groups, more preferably, each R 4 and R 5 Independently 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).

[0054] In some embodiments, R 4 and R 5 Each of C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon groups, more preferably, R 4 and R 5 Each of R 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). In some embodiments, R 4 and R 5 It is an adamantyl group.

[0055] R 4 and R 5 The properties 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 , R5 or R 4 and R 5 When phenyl, the catalyst compound can provide a low molecular weight polymer.

[0056] In at least one embodiment, R of formula (I) 2 and R 7 Each of C1-C 10 Alkyl groups, such as R 2 and R 7 and tert-butyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dimethylpentyl, tert-butyl, isopropyl or an isomer thereof.

[0057] R of formula (I) 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 which can independently be 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 , R 17 , 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 11 , R 12 , R 13 , R 15 and R 16 is hydrogen. Alternatively, R 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R13 , R 15 and R 16 Each of may independently be hydrogen, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy or trimethylsilyl.

[0058] In some embodiments, R 17 , R 18 or R 19 At least one of them is C2-C 40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C 40 Containing heteroatom groups.

[0059] In some embodiments, R 17 , R 18 or R 19 At least one of them is independently C2-C 40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C 40 containing heteroatom groups, and R 17 , R 18 or R 19 At least one of them is hydrogen.

[0060] In some embodiments, R 17 , R 18 or R 19 One of them is independently C2-C 40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C 40 containing heteroatom groups, and R 17 , R 18 or R 19 Two of them are hydrogen.

[0061] In some embodiments, R 18 C2-C 40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C 40 containing heteroatom groups, and R 17 and R 19 For hydrogen.

[0062] In some embodiments, R 17 or R 19 One of them is C2-C 40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C 40 Heteroatom-containing groups, R18 is hydrogen, and R 17 or R 19 One of them is hydrogen.

[0063] In some embodiments, R 17 and R 19 Independently for C2-C 40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C 40 containing heteroatom groups, and R 18 For hydrogen.

[0064] In some embodiments, R 17 , R 18 or R 19 At least one of them is a structural part containing at least two or more saturated or unsaturated carbon atoms, such as C2-C 40 Hydrocarbyl (e.g., ethyl, vinyl, propyl (e.g., n-propyl, isopropyl, cyclopropyl), propenyl, propynyl, butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), butenyl, butynyl, pentyl (e.g., isopentyl, cyclopentyl), pentenyl, pentynyl, hexyl (e.g., cyclohexyl), hexenyl, hexynyl, heptyl, heptenyl, heptynyl, octyl (e.g., cyclooctyl), octenyl, octynyl, nonyl, nonenyl, nonynyl, decyl (e.g., adamantyl), decenyl, decynyl, undecyl, undecenyl, undecynyl, decenyldodecyl, dodecenyl, dodecynyl, tridecyl, tridecenyl, tridecynyl, tetradecyl, tetradecenyl, tetradecynyl, pentadecyl, pentadecenyl, pentadecynyl, hexadecyl, hexadecenyl, hexaynyl, heptadecyl, heptadecenyl, heptaynyl, octadecyl, octadecenyl, octaynyl, nonadecyl, nonadecenyl, nonadeynyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl and isomers thereof), C2-C 40 Substituted hydrocarbon or C2-C 40 Heteroatom-containing groups (e.g., hydrocarbyloxy, trihydrocarbylsilyl, trihydrocarbylgermyl, dihydrocarbylamino, dihydrocarbylphosphino).

[0065] In some embodiments, R containing at least two or more saturated or unsaturated carbon atoms 17 , R 18 and R 19 At least one of the following is a structural moiety containing at least three or more non-hydrogen atoms, such as C3-C 40Hydrocarbyl (e.g., propyl (e.g., n-propyl, isopropyl, cyclopropyl), propenyl, propynyl, butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), butenyl, butynyl, pentyl (e.g., isopentyl, cyclopentyl), pentenyl, pentynyl, hexyl (e.g., cyclohexyl), hexenyl, hexynyl, heptyl, heptenyl, heptynyl, octyl (e.g., cyclooctyl), octenyl, octynyl, nonyl, nonenyl, nonynyl, decyl (e.g., adamantyl), decenyl, decynyl, undecyl, undecenyl, undecynyl, dodecyl, dodecenyl, dodecynyl alkyl, tridecyl, tridecenyl, tridecynyl, tetradecyl, tetradecenyl, tetradecynyl, pentadecyl, pentadecenyl, pentadecynyl, hexadecyl, hexadecenyl, hexadecynyl, heptadecyl, heptadecenyl, heptadecynyl, octadecyl, octadecenyl, octadecynyl, nonadecyl, nonadecenyl, nonadecinyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl and isomers thereof), C2-C 40 Substituted hydrocarbyl (e.g., hydrocarbylenetrihydrocarbylenesilane, hydrocarbylenetrihydrocarbylenegermane, (dihydrocarbylamino)hydrocarbylene, (dihydrocarbylphosphino)hydrocarbylene, (hydrocarbyloxy)hydrocarbylene, (hydrocarbylthio)hydrocarbylene) or C2-C6-C8 ... 40 Heteroatom-containing groups (e.g., hydrocarbyloxy, trihydrocarbylsilyl, trihydrocarbylgermyl, dihydrocarbylamino, dihydrocarbylphosphino).

[0066] In some embodiments, R 17 , R 18 or R 19 At least one of the groups is a moiety containing at least two or more saturated carbon atoms, such as 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), heptyl, 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, triacontyl, and isomers thereof).

[0067] In some embodiments, R 17 , R 18 or R 19at least one of which is a moiety containing at least two or more partially unsaturated carbon atoms, for example, propenyl (e.g., n-propenyl), butenyl (e.g., n-butenyl), pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl (e.g., n-propynyl), butynyl (e.g., n-butynyl), pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl , undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecinyl, octadecynyl, octadecynyl, nonadecinyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, triacontinyl, butadienyl, pentadienyl, hexadienyl, heptadienyl, octadienyl, nonadienyl, decadienyl, undecadienyl, dodecadienyl, substituted phenyl such as methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl and dodecylphenyl and isomers thereof.

[0068] In some embodiments, R 17 , R 18 or R 19 At least one of them is C2-C 40Substituted hydrocarbyl groups include, but are not limited to, hydrocarbylenetrihydrocarbylsilanes (e.g., methylenetrimethylsilane, methylenetriethylsilane, methylenetripropylsilane, methylenetributylsilane, methylenetripentylsilane, methylenetrihexylsilane, methylenedimethylbutylsilane, ethylenetrimethylsilane, ethylenetriethylsilane, ethylenetripropylsilane, ethylenetributylsilane, ethylenetripentylsilane, ethylenetrihexylsilane, ethylenedimethylbutylsilane, and isomers thereof), hydrocarbylenetrihydrocarbylsilanes (e.g., methylenetrimethylsilane, methylenetriethylsilane, methylenetripropylsilane, methylenetributylsilane, ethylenetripentylsilane, ethylenetrihexylsilane, ethylenedimethylbutylsilane, and isomers thereof), trialkylgermanes (e.g., methylenetrimethylgermane, methylenetriethylgermane, methylenetripropylgermane, methylenetributylgermane, methylenetripentylgermane, methylenetrihexylgermane, methylenedimethylbutylgermane, ethylenetrimethylgermane, ethylenetriethylgermane, ethylenetripropylgermane, ethylenetributylgermane, ethylenetripentylgermane, ethylenetrihexylgermane, ethylenedimethylbutylgermane, and isomers thereof), (dialkylamino)alkylene (e.g., (dimethylamino)alkylene 1,2-diamino)methylene, (diethylamino)methylene, (dipropylamino)methylene, (dibutylamino)methylene, (dipentylamino)methylene, (dihexylamino)methylene, (diheptylamino)methylene, (dioctylamino)methylene, (dinonylamino)methylene, (didecylamino)methylene, (henicosylamino)methylene, (didodecylamino)methylene, (methylethylamino)methylene, (dimethylamino)ethylene, (diethylamino)methylene 1,5-Diazabicyclo[3.2.1] oct-8-yl and isomers thereof), (dialkylphosphino)alkylene (e.g., (dimethylphosphino)methylene, (diethylphosphino)methylene, (dipropylphosphino)methylene, (dibutylphosphino)methylene, (dipentyl)phosphinomethylene, (dihexylphosphino)methylene, (diheptylphosphino)methylene, (dioctylphosphino)methylene, (dinonylphosphino)methylene, (didecylphosphino)methylene, (henicosylphosphino)methylene, (docosylphosphino)methylene, ( phosphino)ethylene, (dimethylphosphino)ethylene, (diethylphosphino)ethylene, (dipropylphosphino)ethylene, (dibutylphosphino)ethylene, (dipentyl)phosphinoethylene, (dihexylphosphino)ethylene, (diheptylphosphino)ethylene, (dioctylphosphino)ethylene, (dinonylphosphino)ethylene, (didecylphosphino)methylene, (dihenedecylphosphino)ethylene, (didodecylphosphino)ethylene and isomers thereof), (alkyloxy)alkylene (e.g. methoxymethylene, ethoxy methylene, propoxymethylene, butoxymethylene, pentyloxymethylene, hexyloxymethylene, heptyloxymethylene, octyloxymethylene, nonyloxymethylene, decyloxymethylene, undecyloxymethylene, dodecyloxymethylene, methoxyethylene, ethoxyethylene, propoxyethylene, butoxyethylene, pentyloxyethylene, hexyloxyethylene, heptyloxyethylene, octyloxyethylene, nonyloxyethylene, decyloxyethylene, undecyloxyethylene, dodecyloxyethylene , (phenoxy)methylene, (tolyloxy)methylene, (ethylphenoxy)methylene, (propylphenoxy)methylene, (butylphenoxy)methylene, (pentylphenoxy)methylene, (hexylphenoxy)methylene), 2,6,7-trioxabicyclo[2.2.2]oct-1-yl, 4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl and isomers thereof), (alkylthio)alkylene (e.g., (methylthio)methylene, (ethylthio thio))methylene, (propylthio)methylene, (butylthio)methylene, (pentylthio)methylene, (hexylthio)methylene, (heptylthio)methylene, (octylthio)methylene, (nonylthio)methylene, (decylthio)methylene, (dodecylthio)methylene, (methylthio)ethylene, (ethylthio)ethylene, (propylthio)ethylene, (butylthio)ethylene, (pentylthio)ethylene, (hexylthio)ethylene, (heptylthio)ethylene, (octylthio)ethylene, (nonylthio)ethylene, (decylthio)ethylene, (dodecylthio)ethylene and isomers thereof).

[0069] In some embodiments, R 17 , R 18 or R 19 At least one of them is a C2-C 40Heteroatom-containing groups include, but are not limited to, hydrocarbyloxy (e.g., ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, phenoxy, and substituted phenoxy groups, such as phenoxy-4-(2,4,4-trimethylpentan-2-yl) and (1R,2S,5R)-2-isopropyl-5-methylcyclohexane-1-oxy and isomers thereof), hydrocarbylthio (hydrocarbyl thio) (e.g., ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio, undecylthio, dodecylthio, phenylthio, substituted phenylthio and isomers thereof), trialkylsilyl (e.g., trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, trinonylsilyl, tridecylsilyl, dimethyloctylsilyl, butyldimethylsilyl (including tert-butyldimethylsilyl, n-butyldimethylsilyl) and isomers thereof), trialkylgermyl (e.g., trimethylgermane alkyl, such as dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino, methylethylamino, pyrrolidinyl, piperidinyl and isomers thereof), and dialkylphosphino (such as dimethylphosphino, diethylphosphino, dipropylphosphino, dibutylphosphino, dipentylphosphino, dihexylphosphino, methylethylphosphino, phosphanyl, phosphanyl and isomers thereof).

[0070] In some embodiments of Formula (I), R 4 and R 5 It can be adamantyl or substituted adamantyl, R 2 and R 7 Can be C1-C 20 Hydrocarbyl, and R 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 15 , R 16 , R 17 and R 19 is hydrogen, R 18 It is C2-C 40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C40 Containing heteroatom groups.

[0071] In some embodiments of Formula (I), R 4 and R 5 It can be adamantyl or substituted adamantyl, R 2 and R 7 Can be C1-C 20 Hydrocarbon, R 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 15 , R 16 and R 18 is hydrogen, and R 18 and R 19 One of them is C2-C 40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C 40 containing heteroatom groups, and R 18 and R 19 The other one is hydrogen.

[0072] In some embodiments of Formula (I), R 4 and R 5 It can be adamantyl or substituted adamantyl, R 2 and R 7 Can be C1-C 20 Hydrocarbon, R 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 15 , R 16 and R 18 is hydrogen, and R 18 and R 19 Independently for C2-C 40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C 40 Containing heteroatom groups.

[0073] In some embodiments, R 18 C2-C 40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C40 Containing heteroatom groups.

[0074] In some embodiments, R 18 A linear chain containing at least three non-hydrogen atoms in length and terminally bonded to pyridine.

[0075] In some embodiments, R 17 C2-C 40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C 40 Containing heteroatom groups.

[0076] In some embodiments, R 17 A linear chain containing at least three non-hydrogen atoms in length and terminally bonded to pyridine.

[0077] In some embodiments, R 19 C2-C 40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C 40 Containing heteroatom groups.

[0078] In some embodiments, R 19 A linear chain containing at least three non-hydrogen atoms in length and terminally bonded to pyridine.

[0079] In some embodiments, R 18 Not methyl, methoxy or trifluoromethyl.

[0080] In at least one embodiment, the catalyst compound is one or more of the following:

[0081] 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.

[0082] Other exemplary embodiments of the present technological advancement include the following. A composition of formula (I), wherein R 4 and R 5 is adamantyl, and R 18 C2-C40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C 40 A composition of formula (I), wherein R 4 and R 5 is adamantyl, and R 18 A linear chain containing at least three non-hydrogen atoms in length and terminally bonded to pyridine. A composition of formula (I) wherein R 4 and R 5 is adamantyl, and R 18 Containing the formula A(R a )(R b )(R c ) 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.

[0083] 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), 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 in R 17 , R 18 and R 19 At least two or more saturated or unsaturated carbon atoms, alone or in combination with R 4 and R 5 Substituents and / or R 2 and R 7 The substituents combine to aid in the solubility of the complex of formula (I) in aliphatic solvents.

[0084] 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 40The olefin is contacted with a catalyst system comprising a composition of formula (I) in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form a propylene-based polymer.

[0085] 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 The olefin is contacted with a catalyst system comprising a composition of formula (I) in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form a propylene-based or ethylene-based polymer. Preparation method of transition metal complex

[0086] U.S. patent application Ser. No. 16 / 787,909 (Pub. No. US2020 / 255553) describes a general method for preparing bis(phenolate) ligands and bis(phenolate) complexes that can be used with the present technological advances. Synthesis of substituted pyridine precursors

[0087] The preparation of substituted pyridine precursors may include, but is not limited to, the method shown in Scheme 1. This substituted pyridine precursor can then be used in a method for preparing a bis(phenolate) ligand, as described in U.S. Patent Application Serial No. 16 / 787,909 (Publication No. US2020 / 255553).

[0088] The formation of compound B (method 1) can be accomplished by deprotonating compound A with a strong base such as lithium diisopropylamide (LDA) followed by the addition of a primary or secondary alkyl halide (RX).

[0089] The formation of compound D or E (Method 2) can be accomplished by adding M-OR' or M-SR', respectively, to compound C, wherein M' is a Group 1 element such as Na, and R' is a hydrocarbon group.

[0090] The formation of compound G (Method 3) can be accomplished by adding a Turbo Grinard (eg isopropylmagnesium chloride lithium chloride complex) followed by the addition of a trihydrocarbylsilyl halide (R*3Si-X).

[0091] The formation of compound I by coupling compound G with a substituted aryl lithium compound ("aryl lithium") (Method 4), wherein "aryl" refers to a substituted aryl moiety, can be accomplished by known Pd-catalyzed couplings, such as Negi shi coupling.

[0092] The formation of compound J (method 5) can be accomplished by adding a nucleophile (eg diisopropylamide, substituted aryl oxide) to compound I. Solution 1 Activators and optional scavengers, co-activators and chain transfer agents

[0093] U.S. Patent Application Serial No. 16 / 788,088 (published as US2020 / 254431) 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. US2020 / 044865 (published as WO 2021 / 086467), U.S. Patent Application Serial No. 16 / 394,174 (published as US2019 / 0330394), and PCT Application No. US2019 / 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.

[0094] Although it is preferred to use an activator that is soluble in a non-aromatic hydrocarbon solvent, an activator that is 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.

[0095] 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.

[0096] 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.

[0097] 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

[0098] 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 for combining the catalyst compound and the activator, and / or for introducing the catalyst system or any component thereof into the reactor, and / or for 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.

[0099] 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.

[0100] 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.

[0101] 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 IsopareE TM However, one of ordinary skill in the art may select other suitable non-aromatic hydrocarbon solvents without undue experimentation.

[0102] Highly preferred aliphatic hydrocarbon solvents include isohexane, methylcyclohexane and commercially available solvent mixtures such as Nappa 6 TM and IsoparE TM .

[0103] For compound solubility testing, preferred solvents include isohexane and methylcyclohexane. Optional carrier material

[0104] 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

[0105] 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.

[0106] 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.

[0107] 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 WO2015 / 123177 and WO20 / 092587. blends and films

[0108] 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

[0109] The following chemicals may be abbreviated with lowercase or uppercase letters: 1,2-dimethoxyethane (DME), ethyl ether (Ether), tetrahydrofuran (THF), diatomaceous earth (Celite), methylcyclohexane (MeCy), 1,4-dimethoxyethane (DME), ethyl ether (Ether), tetrahydrofuran (THF), diatomaceous earth (Celite), methylcyclohexane (MeCy), Alkane (di alkane), hexamethyldisiloxane (HMDSO), N,N-dimethylformamide (DMF), N-bromosuccinimide (NBS), n-butyllithium (BuLi). Room temperature is 23°C unless otherwise specified.

[0110] Complexes 1, 2 and 3 (shown below) are comparative complexes. The following chemical substances may be abbreviated with lowercase or uppercase letters: 1,2-dimethoxyethane (DME), ethyl ether (Ether), tetrahydrofuran (THF), diatomaceous earth (Celite), methylcyclohexane (MeCy), 1,4 ...1,4-dimethoxyethane (DME), ethyl ether (Ether), tetrahydrofuran (THF), 1,4-dimethoxyethane (DME), ethyl ether (Ether), tetrahydrofuran (THF), 1,4-dimethoxyethane (DME), ethyl ether (Ether), tetrahydrofuran (THF), 1,4-dimethoxyethane (DME), ethyl ether (Ether), Alkane (di alkane), hexamethyldisiloxane (HMDSO).

[0111] Complexes 1 ([2',2"'-(pyridine-2,6-diyl)bis(3-adamantane-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenol)]dimethylzirconium) and 2 ([2',2"'-(pyridine-2,6-diyl)bis(3-adamantane-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)]dimethylzirconium) were prepared as described in U.S. patent application US2020 / 0255553 A1.

[0112] Unless otherwise stated, all reagents were purchased from commercial suppliers (Sigma Aldrich, Fisher Scientific, Oakwood Chemical, or Combi-Blocks) and used as received. Solvents were sparged with N2 and The mixture was dried over molecular sieves. Lithium diisopropylamide (LDA) was prepared as described in Org. Synth. 1986, v. 64, 68. 2,6-Dibromo-4-nitropyridine and 2,6-dibromo-4-(pyrrolidin-1-yl)pyridine were prepared as described in [Organic Letters, 2010, v. 12 (22), p. 5242-5245]. All chemical manipulations were performed under nitrogen unless otherwise stated. Flash column chromatography was performed using Sigma Aldrich silica gel. (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. Preparation of catalyst precursors and ligands

[0113] ZrCl4(ether)2 Combine dichloromethane (100mL) and ZrCl4 (10.0g, 42.9mmol) to form a slurry. Add ether (9.54g, 129mmol) dropwise over 60 minutes. Stir the mixture for 1 hour. Allow the undissolved solid to settle, then decant the supernatant and filter through diatomaceous earth (Celite) on a sintered disk. Evaporate the filtrate to near dryness to provide a slurry. Add isohexane (60mL) to the slurry and stir the mixture vigorously. The resulting off-white solid is collected on a glass frit, washed with isohexane, and dried under reduced pressure. Yield: 12.5g, 76.6%.

[0114] 2-(2-(1-adamantyl)-4-tert-butylphenoxy)tetrahydro-2H-pyran At -10 ° C, to a solution of 2- (1- adamantyl) -4- (tert-butyl) phenol (38.0g, 133mmol) and 3,4- dihydro -2H- pyran (22.5g, 267mmol) in dichloromethane (300mL) was added p-toluenesulfonic acid monohydrate (203mg, 1.07mmol). The reaction mixture was slowly warmed to ambient temperature and stirred while monitoring the reaction by thin layer chromatography (TLC). After the starting material was completely converted (indicated by TLC, about 5 minutes at ambient temperature), sodium tert-butoxide (128mg, 1.33mmol) was added immediately. The resulting mixture was filtered through a silica gel plug and then washed with a 1: 1 dichloromethane: hexane solution. The combined filtrate was concentrated to give the product as a white solid (46.30g, 94%). 1 H NMR (400MHz, CDCl3) δ7.26 (s, 1H), 7.17-7.08 (m, 2H), 5.46 (s, 1H), 3.92 (t, J = 10.8Hz, 1H), 3. 65(d,J=11.8Hz,1H),2.28-2.00(m,10H),1.99-1.84(m,2H),1.84-1.56(m,9H),1.30(s,9H).

[0115] (3-(1-adamantyl)-5-(tert-butyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)lithium etherate To a solution of 2-(2-(1-adamantyl)-4-tert-butylphenoxy)tetrahydro-2H-pyran (46.3 g, 126 mmol) in diethyl ether (100 mL) was added n-butyllithium (1.6 M, 82.4 mL, 132 mmol) in hexanes at ambient temperature. The solution was stirred for 1 hour and then concentrated to dryness. The crude product was slurried in pentane (30 mL) and stirred for 30 minutes. The product was isolated by filtration as a white solid (40.0 g, 71%). 1 H NMR(400MHz,THF-d8)δ7.73(s,1H),6.86(s,1H),6.59(br,1H),3.91(t,J=11.7Hz,1H),3.55-3.43( m, 1H), 2.27 (q, J = 12.4Hz, 7H), 2.04 (d, J = 18.1Hz, 5H), 1.80 (td, J = 23.8, 13.1Hz, 9H), 1.32 (s, 9H).

[0116] 2-((3-(1-adamantyl)-2'-bromo-5-(tert-butyl)-[1,1'-biphenyl]-2-yl)oxy)tetrahydro-2H-pyran (3-(1-adamantyl)-5-(tert-butyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)lithioetherate (20.1 g, 44.8 mmol) was dissolved in THF (100 mL) and hexanes (100 mL). To the resulting solution was added 2-bromochlorobenzene (9.44 g, 49.4 mmol) in hexanes (50 mL) dropwise at 60°C. The reaction was stirred at 60°C for 1 hour. After the reaction was cooled to room temperature, water (100 mL) was added and the resulting mixture was stirred for 10 minutes. After separation of the two phases, the aqueous phase was extracted with diethyl ether. The combined organic extracts were dried over MgSO4 and then concentrated under vacuum. The product was then precipitated from a minimal amount of pentane as a white solid, which was collected by filtration. The additional product remaining in the filtrate was purified by flash chromatography on silica gel (30% dichloromethane in hexanes). The overall yield was 87% (20.5 g). 1 H NMR (400MHz, CDCl3) δ7.68 (dd, J=30.1, 8.0Hz, 1H), 7.53-7.13 (m, 4H), 7.01 (dd, J=59.7, 2.3Hz, 1H), 4.31 (dd, J=8.1, 2.3Hz, 1H), 3.79 (dd, J=39.7, 12.0Hz,1H),2.99(dt,J=97.6,11.2Hz,1H),2.26(dt,J=22.7,12.8Hz,6H ),2.11(s,3H),1.86-1.50(m,8H),1.47-1.23(m,12H),1.20-1.01(m,1H).

[0117] 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinine To a solution of 2-((3-(1-adamantyl)-2'-bromo-5-(tert-butyl)-[1,1'-biphenyl]-2-yl)oxy)tetrahydro-2H-pyran (23.5 g, 44.9 mmol) in THF (200 mL) was added n-butyllithium (1.6 M, 33.4 mL, 53.5 mmol) in hexanes at -78°C over 20 minutes. The reaction mixture was stirred at -78°C for 1 hour, then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11.8 g, 63.1 mmol) was added. The resulting suspension was stirred at ambient temperature for 1 hour, then poured into 100 mL of water. The resulting mixture was extracted with hexanes (100 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×50 mL). The combined organic extracts were dried over MgSO4 and concentrated to dryness.

[0118] To the resulting residue was added isopropanol (150 mL) and the resulting solution was refluxed for 16 hours. After the reaction was allowed to cool to ambient temperature, the reaction was concentrated and cooled to -20°C for 1 hour to afford the product as a white solid (16.6 g, 80%) which was isolated by filtration. 1 H NMR (400MHz, CDCl3) δ8.17(d,J=8.2Hz,1H),8.09-8.02(m,2H),7.65(t,J=8.0Hz,1H),7.45-7.4 0(m,2H),5.24(p,J=6.1Hz,1H),2.30(br,6H),2.16(br,3H),1.84(br,6H),1.43-1.39(m,15H).

[0119] 2',2"'-(pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)

[0120] Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (3.29 g, 6.91 mmol, 2.1 equiv) was added to 1,4-dibenzo[c,e][1,2]oxaborinane. 2,6-dibromopyridine (0.78 g, 3.29 mmol, 1.0 equiv), cesium carbonate (2.73 g, 19.8 mmol), Buchwald RuPhos PalladacycleGen II precatalyst (Strem, CAS1375325-68-0, 24 mg, 0.03 mmol, 0.01 equiv) and water (3 ml) were added to a solution in 2,6-dibromopyridine (0.78 g, 3.29 mmol, 1.0 equiv), cesium carbonate (2.73 g, 19.8 mmol), Buchwald RuPhos PalladacycleGen II precatalyst (Strem, CAS1375325-68-0, 24 mg, 0.03 mmol, 0.01 equiv) and water (3 ml). The reaction mixture was stirred at 100°C for 15 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with dichloromethane (20 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The crude product was dissolved in hot anhydrous ethanol, which was slowly cooled to ambient temperature and then placed at -20°C for 1 hour. The solid was then filtered to give the product as a mixture of two isomers (1.65 g, 63%).

[0121] 2',2"'-(4-methylpyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.555 g, 1.30 mmol) was added to 1,4-dihydro- 2,6-dichloro-4-methylpyridine (0.100 g, 0.62 mmol), potassium carbonate (0.51 g, 3.70 mmol), Buchwald RuPhos Pal ladacycle Gen I precatalyst (Strem, CAS1028206-60-1, 22.5 mg, 0.03 mmol) and water (2 mL) were added to a solution in 2,6-dichloro-4-methylpyridine (0.100 g, 0.62 mmol), potassium carbonate (0.51 g, 3.70 mmol), Buchwald RuPhos Pal ladacycle Gen I precatalyst (Strem, CAS1028206-60-1, 22.5 mg, 0.03 mmol) and water (2 mL). The reaction mixture was stirred at 100 ° C for 16 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with hexane (10 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×20 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The product (0.46 g, 92%) was purified by flash chromatography on silica gel (30% dichloromethane in hexane) as a mixture of two isomers. 1H NMR (400 MHz, CDCl3) δ 8.27 (s, 2H in A), 7.56-7.34 (m, 8H), 7.07 (s, 2H), 6.97 (s, 1H in B), 6.92 (s, 1H in B), 6.81 (s, 1H in B), 6.78 (s, 1H in B), 6.74 (s, 2H in A), 6.52 (s, 2H in A), 2.13-1.87 (m, 21H), 1.66 (br, 12H), 1.16 (s, 9H in B), 0.99 (s, 9H in A).

[0122] 2,6-Dibromo-4-ethylpyridine A solution of 2,6-dibromo-4-methylpyridine (3.00 g, 12.0 mmol) in THF (5 mL) and a solution of freshly prepared LDA (1.28 g, 12.0 mmol) in THF (3 mL) were cooled separately in a cooling bath at -55 °C for 10 minutes. The cooled LDA solution was then slowly added to the solution of 2,6-dibromo-4-methylpyridine, which was stirred at -55 °C for 1 hour. Iodomethane (1.70 g, 12.0 mmol) was then added to the reaction mixture, which was stirred at ambient temperature for 2 hours. The reactants were then quenched with water and diluted with hexane. After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The product was purified by flash chromatography on silica gel (30% dichloromethane in hexane) with a yield of 67% (2.11 g). 1 H NMR (400MHz, CDCl3) δ7.29 (s, 2H), 2.61 (q, J = 7.6Hz, 2H), 1.24 (td, J = 7.7, 1.2Hz, 3H).

[0123] 2',2"'-(4-ethylpyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (2.10 g, 4.91 mmol) was added to 1,4-dihydro- 2,6-bromo-4-ethylpyridine (0.65 g, 2.45 mmol), potassium carbonate (2.03 g, 14.7 mmol), Buchwald RuPhos Pal ladacycle Gen I precatalyst (Strem, CAS 1028206-60-1, 27.0 mg, 0.04 mmol) and water (6 mL) were added to a solution in 2,6-bromo-4-ethylpyridine (0.65 g, 2.45 mmol), potassium carbonate (2.03 g, 14.7 mmol), Buchwald RuPhos Pal ladacycle Gen I precatalyst (Strem, CAS 1028206-60-1, 27.0 mg, 0.04 mmol) and water (6 mL). The reaction mixture was stirred at 100 ° C for 16 hours, then cooled to ambient temperature and diluted with water (30 mL). The resulting mixture was diluted with hexane (20 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×50 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The product was purified on silica gel by flash chromatography (eluting impurities with 15% dichloromethane in hexane, and then eluting the product with 25% dichloromethane + 2% acetone in hexane). The product (1.59 g, 79%) was isolated as a mixture of two isomers. 1 H NMR (400 MHz, CDCl3) δ 8.29 (s, 2H in A), 7.65-7.34 (m, 8H), 7.14-7.05 (m, 2H), 6.92 (s, 2H in B), 6.81 (s, 2H in B), 6.76 (s, 2H in A), 6.67 (s, 2H in B), 6.53 (s, 2H in A), 2.36 (q, J = 7.5 Hz, 2H), 2.13-1.79 (m, 18H), 1.66 (br, 12H), 1.17 (s, 18H in B), 0.99 (s, 18H in A), 0.93-0.69 (m, 3H).

[0124] 2,6-Dibromo-4-(ethylthio)pyridine At 0 ° C, 260 μL of ethanethiol (3.54 mmol) was added to a suspension of 71 mg NaH (1.77 mmol, 60% by weight dispersion in mineral oil was thoroughly washed with hexane before use) in 5 mL THF. Afterwards, 500 mg of 2,6-dibromo-4-nitropyridine (1.77 mmol) was added at once at 0 ° C. The reaction mixture was warmed to room temperature, then stirred overnight, and finally carefully quenched with 5 mL of water. The resulting mixture was extracted with dichloromethane (3×20 mL), and 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 μm, eluent: hexane-ethyl acetate-dichloromethane=10:1:1, volume). 310 mg (53%) of beige solid was produced. 1H NMR (CDCl3, 400MHz): δ7.22 (s, 2H), 3.01 (q, J = 7.4Hz, 2H), 1.41 (t, J = 7.4Hz, 3H). 13 C NMR (CDCl3, 100MHz) δ153.2, 140.4, 122.7, 25.2, 13.3.

[0125] 2-(Adamantane-1-yl)-6-bromo-4-methylphenol To a solution of 21.2 g (87.0 mmol) of 2-(adamantan-1-yl)-4-methylphenol in 200 mL of dichloromethane was added dropwise 4.50 mL (87.0 mmol) of bromine in 100 mL of dichloromethane over 10 minutes at room temperature. The resulting mixture was diluted with 400 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL), and the combined organic extracts were washed with 5% NaHCO, dried over NaSO, and then evaporated to dryness. 21.5 g (77%) of a white solid was obtained. 1 H NMR (CDCl3, 400MHz): δ7.17(s,1H),6.98(s,1H),5.65(s,1H),2.27(s,3H),2.10-2.13(m,9H),1.80(m,6H), 13 C NMR (CDCl3, 100MHz): δ148.18, 137.38, 130.24, 129.32, 127.26, 112.08, 40.18, 37.32, 36.98, 28.99, 20.55.

[0126] (1-(3-Bromo-5-methyl-2-(methoxymethoxy)phenyl)adamantane To a solution of 21.3 g (66.4 mmol) of 2-(adamantan-1-yl)-6-bromo-4-methylphenol in 400 mL of THF was added portionwise 2.79 g (69.7 mmol, 60 wt % in mineral oil) of sodium hydride at room temperature. To the resulting suspension was added dropwise 5.55 mL (73.0 mmol) of methoxymethyl chloride over 10 minutes at room temperature. The resulting mixture was stirred overnight and then poured into 200 mL of water. The resulting mixture was extracted with dichloromethane (3 x 200 mL), and the combined organic extracts were washed with 5% NaHCO, dried over NaSO, and then evaporated to dryness. 24.3 g (quantitative) of a white solid was produced. 1H NMR (CDCl3, 400MHz): δ7.24 (d, J = 1.5 Hz, 1H), 7.05 (d, J = 1.8 Hz, 1H), 5.22 (s, 2H), 3.71 (s, 3H), 2.27 (s, 3H), 2.05-2.12 (m, 9H), 1.78 (m, 6H). 13 C NMR (CDCl3, 100MHz): δ151.01,144.92,134.34,131.80,127.44,117.57,99.56,57.75,41.27,37.71,36.82,29.03,20.68.

[0127] 2-(3-adamantan-1-yl)-5-methyl-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane To a solution of 20.0 g (55.0 mmol) of (1-(3-bromo-5-methyl-2-(methoxymethoxy)phenyl)adamantane in 400 mL of anhydrous THF at -80°C, 22.5 mL (56.4 mmol) of 2.5 M 2-(methoxymethoxy)phenyl)adamantane was added dropwise over 20 minutes. n BuLi. The reaction mixture was stirred at this temperature for 1 hour, then 16.7 mL (82.2 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. The crude product was extracted with dichloromethane (3×300 mL), the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. 22.4 g (99%) of a colorless viscous oil were obtained. 1 H NMR (CDCl3, 400MHz): δ7.35 (d, J = 2.3Hz, 1H), 7.18 (d, J = 2.3Hz, 1H), 5.14 (s, 2H) ,3.58(s,3H),2.28(s,3H),2.14(m,6H),2.06(m,3H),1.76(m,6H),1.35(s,12H). 13 C NMR (CDCl3, 100MHz): δ159.68,141.34,134.58,131.69,131.14,100.96,83.61,57.75,41.25,37.04,29.14,24.79,20.83.

[0128] 1-(2'-bromo-5-methyl-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane Then, 10.0 g (24.3 mmol) of 2-(3-adamantan-1-yl)-5-methyl-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added to 100 mL of 1,4-dioxaborolane. 7.22 g (25.5 mmol) of 2-bromoiodobenzene, 8.38 g (60.6 mmol) of potassium carbonate and 50 mL of water were added to the solution in alkane. The obtained mixture was purged with argon for 10 minutes, and then 1.40 g (1.21 mmol) of Pd (PPh 3 ) 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 crude product was extracted with dichloromethane (3×150 mL), and the combined organic extracts were dried over Na 2 SO 4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, volume). 10.7 g (quantitative) of white solid was produced. 1 H NMR (CDCl3, 400MHz): δ7.72 (d, J = 7.9Hz, 1H), 7.35-7.44 (m, 3H), 7.19-7.26 (m, 1H), 6.94 (m, 1H) ,4.53(dd,J=20.0,4.6Hz,2H),3.24(s,3H),2.38(s,3H),2.23(m,6H),2.15(m,3H),1.84(m,6H). 13 C NMR (CDCl3, 100MHz): δ151.51,142.78,141.11,134.63,132.76,132.16,132.13,129. 83,128.57,127.76,127.03,124.05,98.85,56.95,41.21,37.18,36.94,29.07,21.00.

[0129] 4-((3r,5r,7r)-adamantan-1-yl)-6-isopropoxy-2-methyl-6H-dibenzo[c,e][1,2]oxaborinane To a solution of 5.45 g (12.3 mmol) of 1-(2'-bromo-5-methyl-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane in 100 mL of dry THF at -80°C was added dropwise 5.92 mL (14.8 mmol) of 2.5 M 2-(methoxymethoxy)-1-(1,1'-biphenyl)-3-yl)adamantane over 20 minutes. nBuLi. The reaction mixture was stirred at this temperature for 1 hour, then 3.78 mL (18.5 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The resulting suspension was stirred at room temperature for 1 hour, then poured into 300 mL of water. The crude product was extracted with dichloromethane (3×100 mL), and the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residue was refluxed in 100 mL of isopropanol for 4 hours. The precipitated crystals were filtered off on a glass frit (G4) and dried in vacuo. 3.75 g (79%) of a white crystalline solid was produced. 1 H NMR (CDCl3, 400MHz): δ8.18(d,J=8.3Hz,1H),8.12(dd,J=7.5,1.1Hz,1H),7.88(s,1H),7.67(dt,J=7.5,1.5Hz,1H),7.45(dt,J=7.4,0.7Hz,1H ),7.21(d,J=1.8Hz,1H),5.29(sept,J=6.2Hz,1H),2.48(s,3H),2.30-2.35(m,6H),2.20(br.s,3H),1.85-1.90(m,6H),1.46(d,J=6.2Hz,6H). 13 C NMR (CDCl3, 100MHz): δ148.4,140.6,139.3,133.0,131.8,130.7,127.5,126.6,122.8,121.9,121.6,65.7,40.7,37.15,37.12,29.1,24.7,21.4.

[0130] 2',2"'-(4-(ethylthio)pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenol) Then, 770 mg (2.00 mmol) of 4-((3r,5r,7r)-adamantan-1-yl)-6-isopropoxy-2-methyl-6H-dibenzo[c,e][1,2]oxaborinane was dissolved in 5 mL of 1,4-dihydro- 290mg (0.98mmol) 2,6-dibromo-4-(ethylthio)pyridine, 1.63g (5.00mmol) cesium carbonate and 3mL water were added to the solution in alkane. The obtained mixture was purged with argon for 1 minute, and then 112mg (0.10mmol) Pd (PPh3) 4 was added. This mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 50mL water. The mixture thus obtained was extracted with dichloromethane (3×50ml), and the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63μm, eluent: hexane-dichloromethane = 1:1, volume). 580mg (77%) of a mixture of two isomers was produced as a colorless glassy solid. 1 H NMR (CDCl3, 400MHz): δ7.65(s,1H),7.58-7.62(m,2H),7.45-7.51(m,4H),7.32-7.41(m,3H),6.92(s,1H),6.86-6.88(m, 2H),6.79-6.81(m,2H),6.21(s,1H),2.41-2.70(m,2H),2.26(s,3H),2.00(s,3H),1.57-1.98(m,30H),1.14-1.20(m,3H). 13 C NMR(CDCl3,100MHz)δ157.3,157.2,151.3,150.3,150.2,149.7,139.5,138.3 ,138.0,137.9,137.6,137.5,132.4,131.3,130.4,130.2,130.15,129.5,129. 0,128.8,128.6,127.83,127.76,127.0,126.7,119.6,118.6,40.5,40.1,37.09,37.03,36.83,36.75,36.5,29.1,29.0,25.0,24.6,20.8,20.6,13.6,13.4.

[0131] 2,6-Dichloro-4-butylpyridine A solution of 2,6-dichloro-4-methylpyridine (5.00 g, 30.9 mmol) in THF (10 mL) and a solution of freshly prepared LDA (3.31 g, 30.9 mmol) in THF (5 mL) were cooled in a cooling bath at -55 ° C for 10 minutes. The cooled LDA solution was then slowly added to the solution of 2,6-dichloro-4-methylpyridine, which was stirred at -55 ° C for 1 hour. 1-Bromopropane (3.80 g, 30.9 mmol) was then added to the reaction mixture, which was stirred at ambient temperature for 12 hours. The reactants were then quenched with water and diluted with hexane. After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The product was purified by flash chromatography on silica gel (20% dichloromethane in hexane) to give a 74% yield (4.63 g). 1 H NMR (400MHz, CDCl3) δ7.08 (s, 2H), 2.59 (t, J = 7.8Hz, 2H), 1.60 (p, J = 7.4Hz, 2H), 1.35 (h, J = 7.4Hz, 2H), 0.93 (td, J = 7.3, 1.4Hz, 3H).

[0132] 2',2"'-(4-butylpyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (2.97 g, 6.39 mmol) was added to 1,4-dihydro- 2,6-dichloro-4-butylpyridine (0.69 g, 3.38 mmol), cesium carbonate (6.61 g, 20.2 mmol), Buchwald RuPhos Palladacycle Gen I precatalyst (Strem, CAS1028206-60-1, 60.0 mg, 0.08 mmol) and water (10 mL) were added to a solution in 2,6-dichloro-4-butylpyridine (0.69 g, 3.38 mmol), cesium carbonate (6.61 g, 20.2 mmol), Buchwald RuPhos Palladacycle Gen I precatalyst (Strem, CAS1028206-60-1, 60.0 mg, 0.08 mmol) and water (10 mL). The reaction mixture was stirred at 100 ° C for 16 hours, then cooled to ambient temperature and diluted with water (30 mL). The resulting mixture was diluted with hexane (20 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×50 mL). The combined organic extracts were dried over MgSO4 and filtered on a small amount of silica gel and then concentrated to dryness. The crude product was dissolved in hexane and ethanol (100 mL) was subsequently added. The solution was concentrated under reduced pressure at 40 ° C and then allowed to cool to ambient temperature. The precipitate was isolated as the ethanol adduct, which was dissolved in toluene and concentrated to dryness to remove all ethanol. The product (1.95 g, 35%) was isolated as a mixture of two isomers. 1 HNMR (400 MHz, CDCl3) δ8.29 (s, 2H in A), 7.59-7.35 (m, 8H), 6.94 (s, 2H in B), 6.80 (s, 2H in B), 6.75 (m), 6.56-6.53 (s, 2H), 2.35-2.19 (m, 2H), 2.06-1.85 (m, 18H), 1.66 (br, 12H), 1.25-1.17 (m, 4H), 1.17 (s, 9H in B), 1.00 (s, 9H in A), 0.86 (t, J = 6.8 Hz, 3H).

[0133] 2,6-Dichloro-4-((tert-butyldimethylsilyl)methyl)pyridine A solution of 2,6-dichloro-4-methylpyridine (1.00 g, 6.17 mmol) in THF (3 mL) and a solution of freshly prepared LDA (0.661 g, 6.17 mmol) in THF (2 mL) were cooled in a cooling bath at -55 °C for 10 minutes. The cooled LDA solution was then slowly added to the solution of 2,6-dichloro-4-methylpyridine, which was stirred at -55 °C for 1 hour. Tert-butyldimethylsilyl chloride (0.93 g, 6.17 mmol) was then added to the reaction mixture, which was stirred at ambient temperature for 2 hours. The reactants were then quenched with water and diluted with hexane. After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The product was purified by flash chromatography on silica gel (20% dichloromethane in hexane) to give a 94% yield (1.61 g). 1 H NMR (400MHz, CDCl3) δ6.89 (s, 2H), 2.10 (s, 2H), 0.92 (d, J = 1.5Hz, 9H), -0.06 (d, J = 1.3Hz, 6H).

[0134] 2',2"'-(4-((tert-butyldimethylsilyl)methyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.62 g, 1.45 mmol) was added to 1,4-dihydro- 2,6-dichloro-4-((tert-butyldimethylsilyl)methyl)pyridine (0.20 g, 0.72 mmol), potassium carbonate (0.600 g, 4.3 mmol), Buchwald RuPhosPal ladacycle Gen I precatalyst (Strem, CAS1028206-60-1, 7.9 mg, 0.01 mmol) and water (2 mL) were added to a solution in 2,6-dichloro-4-((tert-butyldimethylsilyl)methyl)pyridine (0.20 g, 0.72 mmol), potassium carbonate (0.600 g, 4.3 mmol), Buchwald RuPhosPal ladacycle Gen I precatalyst (Strem, CAS1028206-60-1, 7.9 mg, 0.01 mmol) and water (2 mL). The reaction mixture was stirred at 100 ° C for 16 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with hexane (10 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×20 mL). The combined organic extracts were dried over MgSO4 and filtered over a small amount of silica gel and then concentrated to dryness. The product was purified by flash chromatography on silica gel (impurities eluted with 15% dichloromethane in hexanes, then the product eluted with 25% dichloromethane + 2% acetone in hexanes) to give the product in 55% yield (0.31 g).1 H NMR (400 MHz, CDCl3) δ 8.21 (s, 2H in A), 7.58-7.30 (m, 8H), 7.09 (d, J = 2.4 Hz, 2H), 7.00 (d, J = 2.4 Hz, 2H in B), 6.73 (s, 2H in B), 6.67 (s, 2H in B), 6.59 (s, 2H in A), 6.57 (s, 2H in A), 2.16-1.80 (m, 18H), 1.76-1.60 (m, 12H), 1.37-1.23 (m, 2H) 1.18 (s, 18H in B), 1.03 (s, 18H in A), 0.87 (s, 9H), -0.18 (s, 6H in A), -0.23 (s, 6H in B).

[0135] 2,6-Dichloro-4-((triethylsilyl)methyl)pyridine A solution of 2,6-dichloro-4-methylpyridine (1.00 g, 6.17 mmol) in THF (3 mL) and a solution of freshly prepared LDA (0.661 g, 6.17 mmol) in THF (2 mL) were cooled in a cooling bath at -55 °C for 10 minutes. The cooled LDA solution was then slowly added to the solution of 2,6-dichloro-4-methylpyridine, which was stirred at -55 °C for 1 hour. Triethylsilyl chloride (0.93 g, 6.17 mmol) was then added to the reaction mixture, which was stirred at ambient temperature for 2 hours. The reactants were then quenched with water and diluted with hexane. After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The product was purified by flash chromatography on silica gel (20% dichloromethane in hexane) to give a 94% yield (1.61 g). 1 H NMR (400MHz, CDCl3) δ6.89 (s, 2H), 2.11 (s, 2H), 0.93 (t, J = 7.9Hz, 9H), 0.54 (q, J = 7.9Hz, 6H).

[0136] 2',2"'-(4-((triethylsilyl)methyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.50 g, 1.17 mmol) was added to 1,4-dihydro- 2,6-dichloro-4-((triethylsilyl)methyl)pyridine (0.26 g, 0.58 mmol), potassium carbonate (0.485 g, 3.5 mmol), Buchwald RuPhos Palladacycle Gen I precatalyst (Strem, CAS1028206-60-1, 4.3 mg, 0.005 mmol) and water (2 mL) were added to a solution in 1,6-dichloro-4-((triethylsilyl)methyl)pyridine (0.26 g, 0.58 mmol), potassium carbonate (0.485 g, 3.5 mmol), Buchwald RuPhos Palladacycle Gen I precatalyst (Strem, CAS1028206-60-1, 4.3 mg, 0.005 mmol) and water (2 mL). The reaction mixture was stirred at 100 ° C for 16 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with hexane (10 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×20 mL). The combined organic extracts were dried over MgSO4 and filtered over a small amount of silica gel and then concentrated to dryness. The product was purified by flash chromatography on silica gel (eluting the impurities with 15% dichloromethane in hexanes, then eluting the product with 25% dichloromethane + 2% acetone in hexanes). The product was isolated (0.46 g, 72%) as a mixture of two isomers. 1 H NMR (400 MHz, CDCl3) δ 8.28 (s, 2H in A), 7.60-7.31 (m, 8H), 7.07 (s, 2H), 6.80 (s, 1H in B), 6.74 (s, 1H in B), 6.63 (s, 2H in B), 6.61 (s, 2H in A), 6.57 (s, 2H in B), 6.54 (s, 2H in A), 2.26-1.72 (m, 20H), 1.65 (br, 12H), 1.17 (s, 18H in B), 1.01 (s, 18H in A), 0.86 (t, J = 7.8 Hz, 9H), 0.42 (q, J = 7.9 Hz, 6H).

[0137] 2,6-Dichloro-4-((trihexylsilyl)methyl)pyridine A solution of 2,6-dichloro-4-methylpyridine (1.00 g, 6.17 mmol) in THF (3 mL) and a solution of freshly prepared LDA (0.661 g, 6.17 mmol) in THF (2 mL) were cooled in a cooling bath at -55 °C for 10 minutes. The cooled LDA solution was then slowly added to the solution of 2,6-dichloro-4-methylpyridine, which was stirred at -55 °C for 1 hour. Triethylsilyl chloride (0.93 g, 6.17 mmol) was then added to the reaction mixture, which was stirred at ambient temperature for 2 hours. The reactants were then quenched with water and diluted with hexane. After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The product was purified by flash chromatography on silica gel (20% dichloromethane in hexane) to give a 94% yield (1.61 g). 1 H NMR (400MHz, CDCl3) δ6.87 (s, 2H), 2.10 (s, 2H), 1.26 (d, J = 4.6Hz, 24H), 0.88 (t, J = 6.6Hz, 9H), 0.51 (d, J = 10.0Hz, 6H).

[0138] 2',2"'-(4-((trihexylsilyl)methyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.50 g, 1.17 mmol) was added to 1,4-dihydro- 2,6-dichloro-4-((trihexylsilyl)methyl)pyridine (0.26 g, 0.58 mmol), potassium carbonate (0.485 g, 3.5 mmol), Buchwald RuPhos Palladacycle Gen I precatalyst (Strem, CAS1028206-60-1, 4.3 mg, 0.005 mmol) and water (2 mL) were added to a solution in 1,6-dichloro-4-((trihexylsilyl)methyl)pyridine (0.26 g, 0.58 mmol), potassium carbonate (0.485 g, 3.5 mmol), Buchwald RuPhos Palladacycle Gen I precatalyst (Strem, CAS1028206-60-1, 4.3 mg, 0.005 mmol) and water (2 mL). The reaction mixture was stirred at 100 ° C for 16 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with hexane (10 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×20 mL). The combined organic extracts were dried over MgSO4 and filtered over a small amount of silica gel and then concentrated to dryness. The product was purified by flash chromatography on silica gel (eluting the impurities with 15% dichloromethane in hexanes, then eluting the product with 25% dichloromethane + 2% acetone in hexanes). The product was isolated (0.46 g, 72%) as a mixture of two isomers. 1 H NMR (400MHz,CDCl3)δ8.51(s,2H in A),7.62-7.33(m,8H),7.16(s,2H),7.09(s,1H in B),6.88(s,1H in B),6.84(s,2H in B),6.66(s,2H in A),6.60(s,2H in A)i,2.31-1.93(m,20H), 1.86 (br, 6H in A), 1.73 (br, 6H in B), 1.31 (br, 24H), .1.24 (s, 18H in B), 1.08 (s, 18H in A), 0.93 (t, J = 6.6 Hz, 9H), 0.69 (dd, J = 9.5, 6.1 Hz, 6H in B), 0.53 (dd, J = 10.6, 5.2 Hz, 6H in A).

[0139] 2',2"'-(4-(Pyrrolidin-1-yl)pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenol) Then, 2.00 g (5.18 mmol) of 4-((3r,5r,7r)-adamantan-1-yl)-6-isopropoxy-2-methyl-6H-dibenzo[c,e][1,2]oxaborinane was added to 13 mL of 1,4-dihydro- 792mg (2.59mmol) 2,6-dibromo-4-(pyrrolidin-1-yl) pyridine, 4.22g (12.9mmol) cesium carbonate and 7mL water were added to the solution in alkane. The obtained mixture was purged with argon for 10 minutes, and then 299mg (0.260mmol) Pd (PPh3) 4 was added. This mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 50mL water. The mixture thus obtained was extracted with dichloromethane (3×50ml), and the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63μm, eluent: hexane-ethyl acetate = 10:1, volume). The obtained glassy solid was ground with 30mL n-pentane, and the precipitate thus obtained was filtered out (G3), washed with 2×10mL n-pentane, and dried in a vacuum. Yielded 990 mg (47%) of a mixture of two isomers as a white powder. 1 H NMR (CDCl3, 400 MHz): δ 8.65 (br.s, 2H in B), 8.21 (br.s, 2H in A), 7.64-7.66 (m, 2H in A), 7.57-7.59 (m, 2H in B), 7.40-7.49 (m, 4H in A, 4H in B), 7.26-7.34 (m, 2H in A, 2H in B), 6.84-6.89 (m, 3H in A, 3H in B), 6.27 (s, 2H in B), 6.06 (s, 2H in A), 5.99 (s, 2H in A), 2.95-3.10 (m, 4H in A), 2.80-2.93 (m, 4H in B), 2.24 (s, 6H in A), 2.00 (s, 6H in B), 1.50-1.99 (m, 30H in A, 30H in B). 13 C NMR(CDCl3,100MHz)δ157.25,157.18*,150.6,150.2*,140.3*,139.1,138.1*,137 .9,137.7,137.6*,132.2,131.4*,130.8*,130.1,130.0,129.1,129.0,128.98,128 .4*,128.3,128.2*,127.5,127.4*,126.5,126.3*,105.9*,105.7,47.0*,46.7,40.5*,40.1,37.0*,36.8,36.7*,36.4,29.1,29.0,25.33,25.27,25.0*,20.8,20.6*.

[0140] 2,6-Dichloro-4-(tert-butoxy)pyridine A solution of sodium tert-butoxide (0.259 g, 2.69 mmol) in THF (3 mL) and a solution of 2,6-dichloro-4-nitropyridine (0.500 g, 2.59 mmol) in THF (4 mL) were cooled in a cooling bath at 0 ° C for 10 minutes. The cooled sodium tert-butoxide solution was then slowly added to the 2,6-dichloro-4-nitropyridine solution, which was stirred at 0 ° C for 10 minutes. The reaction mixture was then stirred at 40 ° C for another 16 hours. After cooling to ambient temperature, the mixture was quenched with aqueous sodium bicarbonate solution (5 mL). The resulting mixture was diluted with hexane (10 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated. The crude product was filtered over a silica gel plug. After vacuum drying, the pure product (0.550 g, 97%) was isolated as a white solid. 1 H NMR (400MHz, CDCl3) δ6.82 (s, 2H), 1.49 (s, 9H).

[0141] 2',2"'-(4-(tert-Butyloxy)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.584 g, 1.36 mmol) was added to 1,4-dihydro- 2,6-dichloro-4-(tert-butoxy)pyridine (0.150 g, 0.68 mmol), cesium carbonate (1.33 g, 4.09 mmol), Buchwald RuPhos Palladacycle GenII precatalyst (Strem, CAS1375325-68-0, 7.8 mg, 0.01 mmol) and water (3 mL) were added to a solution in 2,6-dichloro-4-(tert-butoxy)pyridine (0.150 g, 0.68 mmol), cesium carbonate (1.33 g, 4.09 mmol), Buchwald RuPhos Palladacycle GenII precatalyst (Strem, CAS1375325-68-0, 7.8 mg, 0.01 mmol) and water (3 mL). The reaction mixture was stirred at 100 ° C for 16 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with hexane (10 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. Purification by flash chromatography on silica gel (50% dichloromethane in hexane) gave the product (0.576 g, 97.3%) as a mixture of two isomers. 1H NMR (400 MHz, CDCl3) δ 8.40 (s, 2H in A), 7.68-7.31 (m, 8H), 7.09 (s, 2H), 7.00 (s, 2H in B), 6.89 (s, 2H in B), 6.68 (s, 2H in B), 6.66-6.46 (m, 4H), 2.09-1.83 (m, 18H), 1.68 (br, 12H), 1.22 (s, 18H in B), 1.16 (s, 9H), 1.05 (s, 18H in A).

[0142] 2,6-Dichloro-4-(3-butenyl)pyridine A solution of 2,6-dichloro-4-methylpyridine (0.700 g, 4.32 mmol) in THF (3 mL) and a solution of freshly prepared LDA (0.509 g, 4.75 mmol) in THF (2 mL) were cooled in a cooling bath at -55 ° C for 10 minutes. The cooled LDA solution was then slowly added to the solution of 2,6-dichloro-4-methylpyridine, which was then stirred at -55 ° C for 1 hour. 3-Bromoprop-1-ene (0.575 g, 12.0 mmol) was then added to the reaction mixture, which was stirred at ambient temperature for 2 hours. The reactants were then quenched with water and diluted with hexane. After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. Purification by flash chromatography on silica gel (20% dichloromethane in hexanes) gave the product in 70% yield (0.610 g). 1 H NMR (400MHz, CDCl3) δ7.07 (s, 2H), 5.91-5.63 (m, 1H), 5.14-4.83 (m, 2H), 2.67 (t, J = 7.7Hz, 2H), 2.35 (q, J = 7.5Hz, 2H).

[0143] 2',2"'-(4-(3-Butenyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.848 g, 1.98 mmol) was added to 1,4-dihydro- 2,6-dichloro-4-(3-butenyl)pyridine (0.200 g, 0.99 mmol), cesium carbonate (1.93 g, 5.94 mmol), Buchwald RuPhos Pal ladacycleGen I precatalyst (Strem, CAS 1028206-60-1, 28.8 mg, 0.04 mmol) and water (3 mL) were added to a solution in 2,6-dichloro-4-(3-butenyl)pyridine (0.200 g, 0.99 mmol), cesium carbonate (1.93 g, 5.94 mmol), Buchwald RuPhos Pal ladacycleGen I precatalyst (Strem, CAS 1028206-60-1, 28.8 mg, 0.04 mmol) and water (3 mL). The reaction mixture was stirred at 100 ° C for 16 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with hexane (10 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×20 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. Purification by flash chromatography on silica gel (50% dichloromethane in hexane) gave 0.36 g (43.4%) of the product as a mixture of two isomers. 1 H NMR (400 MHz, CDCl3) δ 8.22 (s, 2H in A), 7.64-7.30 (m, 8H), 7.09 (s, 2H), 6.92 (s, 2H in B), 6.81 (s, 2H in B), 6.76 (s, 2H in A), 6.53 (s, 2H), 5.66 (td, J = 16.9, 7.0 Hz, 1H), 5.05-4.79 (m, 2H), 2.40 (t, J = 8.0 Hz, 2H), 2.06-1.83 (m, 20H), 1.66 (br, 12H), 1.16 (s, 18H in B), 0.99 (s, 18H in A).

[0144] 2,6-Dichloro-4-propylpyridine A solution of 2,6-dichloro-4-methylpyridine (2.00 g, 12.3 mmol) in THF (5 mL) and a solution of freshly prepared LDA (1.45 g, 13.6 mmol) in THF (3 mL) were cooled in a cooling bath at -55 ° C for 10 minutes. The cooled LDA solution was then slowly added to the solution of 2,6-dichloro-4-methylpyridine, which was stirred at -55 ° C for 1 hour. Ethyl bromide (1.48 g, 13.6 mmol) was then added to the reaction mixture, which was stirred at ambient temperature for 2 hours. The reactants were then quenched with water and diluted with hexane. After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The product was purified by flash chromatography on silica gel (20% dichloromethane in hexane) to give a 69% yield (1.610 g). 1H NMR (400MHz, CDCl3) δ7.07 (d, J = 1.6 Hz, 2H), 2.56 (t, J = 7.7 Hz, 2H), 1.65 (q, J = 8.3, 7.7 Hz, 2H), 0.95 (td, J = 7.4, 1.6 Hz, 3H).

[0145] 2',2"'-(4-propylpyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.225 g, 0.53 mmol) was added to 1,4-dihydro- 2,6-dichloro-4-propylpyridine (0.050 g, 0.26 mmol), cesium carbonate (0.514 g, 1.58 mmol), Buchwald RuPhos Pal ladacycle Gen I precatalyst (Strem, CAS1028206-60-1, 7.8 mg, 0.01 mmol) and water (2 mL) were added to a solution in 2,6-dichloro-4-propylpyridine (0.050 g, 0.26 mmol), cesium carbonate (0.514 g, 1.58 mmol), Buchwald RuPhos Pal ladacycle Gen I precatalyst (Strem, CAS1028206-60-1, 7.8 mg, 0.01 mmol) and water (2 mL). The reaction mixture was stirred at 100 ° C for 16 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with hexane (10 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. Purification by flash chromatography on silica gel (50% dichloromethane in hexane) gave the product (0.100 g, 45.4%) as a mixture of two isomers. 1 H NMR (400 MHz, CDCl3) δ 8.26 (s, 2H in A), 7.64-7.30 (m, 8H), 7.07 (s, 2H), 6.95 (s, 1H in B), 6.92 (s, 1H in B), 6.83 (s, 1H in B), 6.79 (s, 1H in B), 6.75 (s, 2H in A), 6.66 (s, 2H in B) )6.54(s, 2H in A),2.28(t, J=7.8Hz, 2H),2.15-1.84(m, 18H),1.66(br, 12H),1.20(s, 9H in B),1.16(s, 9H in B),0.99(s, 18H in A),0.90-0.82(m, 2H),0.78(t, J=7.1Hz, 3H).

[0146] 2,6-Dichloro-4-(tert-butyldimethylsilyl)pyridine A solution of isopropylmagnesium chloride lithium chloride complex in THF (1.3M, 2.81mL, 3.65mmol) and a solution of 2,6-dichloro-4-iodopyridine (0.550g, 3.65mmol) in THF (5mL) were cooled in a cooling bath at -20°C for 10 minutes. The cooled isopropylmagnesium chloride solution was then slowly added to the solution of 2,6-dichloro-4-iodopyridine, which was then stirred at -20°C for 1 hour. The reaction mixture was then stirred at ambient temperature for another 1 hour. Tert-butyldimethylsilyl chloride (0.550g, 3.65mmol) was then added. The reaction mixture was stirred for 16 hours and then quenched with aqueous sodium bicarbonate solution (5mL). The resulting mixture was diluted with hexane (10mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10mL). The combined organic extracts were dried over MgSO4 and then concentrated. The crude product was dissolved in hot ethanol. The pure product (0.340 g, 36%) was isolated after recrystallization as a white solid. 1 H NMR (400MHz, CDCl3) δ7.29 (s, 2H), 0.89 (s, 9H), 0.30 (s, 6H).

[0147] 2',2"'-(4-(tert-butyldimethylsilyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.584 g, 1.36 mmol) was added to 1,4-dihydro- 2,6-dichloro-4-(tert-butyldimethylsilyl)pyridine (0.179 g, 0.68 mmol), cesium carbonate (1.33 g, 4.09 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 20.0 mg, 0.03 mmol) and water (3 mL) were added to a solution in 2,6-dichloro-4-(tert-butyldimethylsilyl)pyridine (0.179 g, 0.68 mmol), cesium carbonate (1.33 g, 4.09 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 20.0 mg, 0.03 mmol) and water (3 mL). The reaction mixture was stirred at 100 ° C for 5 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with dichloromethane (20 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The crude product was stirred in ethanol at 80 ° C until a white solid precipitate was observed. The resulting mixture was then stored at -20 °C for 1 hour before being filtered to give the product (0.483 g, 78%) as a mixture of two isomers. 1 H NMR (400 MHz, CDCl3) δ 7.94 (s, 2H in A), 7.60-7.38 (m, 8H), 7.14 (d, J = 2.5 Hz, 2H in B), 7.11-7.08 (m, 2H), 7.07 (s, 2H in A), 7.04 (d, J = 2.4 Hz, 2H in B), 6.59 (d, J = 2.4 Hz, 2H in A), 6.32 (s, 2H in B), 2.09-1.86 (m, 18H), 1.68 (br, 12H), 1.23 (s, 18H in B), 1.02 (s, 18H in A), 0.76 (s, 9H), 0.07 (s, 3H in A), 0.01 (s, 6H in B), -0.07 (s, 3H in A).

[0148] 2,6-Dichloro-4-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)pyridine Sodium hydride (0.192 g, 8.00 mmol, 90% pure dry powder) was added to a stirred solution of 4-(1,1,3,3-tetramethylbutyl)phenol (1.50 g, 7.24 mmol) in diethyl ether (10 mL) at 0°C. The mixture was then stirred at ambient temperature for 3 hours. The solvent was removed under vacuum. Sodium 4-(1,1,3,3-tetramethylbutyl)phenol (1.65 g, 99%) was recovered as a white solid. A solution of sodium 4-(1,1,3,3-tetramethylbutyl)phenol (0.592 g, 2.59 mmol) in THF (3 mL) and a solution of 2,6-dichloro-4-nitropyridine (0.500 g, 2.59 mmol) in THF (4 mL) were cooled in a cooling bath at 0°C for 10 minutes. The cooled sodium 4-(1,1,3,3-tetramethylbutyl)phenol solution was then slowly added to the solution of 2,6-dichloro-4-nitropyridine, which was stirred at 0°C for 10 minutes. The reaction mixture was then stirred at 50°C for another 16 hours. After cooling to ambient temperature, the reaction mixture was quenched with aqueous sodium bicarbonate solution (5mL). The resulting mixture was diluted with hexane (10mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The crude product was precipitated from methanol, and the resulting mixture was placed at -30°C for 1 hour. The pure product was isolated by filtration as a white solid (0.700g, 77%). 1 H NMR (400MHz, CDCl3) δ7.47 (d, J = 8.8 Hz, 2H), 7.01 (d, J = 8.8 Hz, 2H), 6.77 (s, 2H), 1.78 (s, 2H), 1.43 (s, 6H), 0.76 (s, 9H).

[0149] 2',2"'-(4-(4-(2,4,4-trimethylpentane-2-yl)phenoxy)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.584 g, 1.36 mmol) was added to 1,4-dihydro- 2,6-dichloro-4-(4-(2,4,4-trimethylpentane-2-yl)phenoxy)pyridine (0.240 g, 0.68 mmol), cesium carbonate (1.33 g, 4.09 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 20.0 mg, 0.03 mmol) and water (3 mL) were added to a solution in 1,2-dichloro-4-(4-(2,4,4-trimethylpentane-2-yl)phenoxy)pyridine (0.240 g, 0.68 mmol), cesium carbonate (1.33 g, 4.09 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 20.0 mg, 0.03 mmol) and water (3 mL). The reaction mixture was stirred at 100°C for 16 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with hexane (10 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. Purification by flash chromatography on silica gel (50% dichloromethane in hexanes) gave 0.637 g (93.4%) of the product as a mixture of two isomers. 1 H NMR (400 MHz, CDCl3) δ 8.24 (s, 2H in A), 7.45-7.30 (m, 10H), 7.08 (s, 2H), 6.95 (s, 2H in B), 6.86-6.77 (m, 2H), 6.62 (s, 2H in B), 6.59 (s, 2H in A), 6.54 (s, 2H), 1.97-1.79 (m, 18H), 1.75-1.55 (m, 14H), 1.36 (br, 6H), 1.16 (s, 18H in B), 1.08 (s in 18H in A), 0.71 (s, 9H).

[0150] 4-(tert-Butyl)thio-2,6-dichloropyridine To a precooled, stirred solution of 2,6-dichloro-4-nitro-pyridine (0.300 g, 1.55 mmol) in tetrahydrofuran was added 2-methylpropane-2-thiolate sodium (0.180 g, 1.61 mmol, 1.03 equivalents). The reaction was stirred at room temperature for 3 hours. The reaction was allowed to settle and the supernatant was decanted into a separate vial. The decant was then concentrated under a nitrogen stream and under high vacuum. The residue was extracted with pentane (10 mL) and filtered on diatomaceous earth (Celite). The filtrate was concentrated under a nitrogen stream and then concentrated under high vacuum to obtain the product, which was a yellow oil that formed white to colorless crystals (0.246 g) after cooling in a refrigerator. The pentane-insoluble solids collected on diatomaceous earth (Celite) were extracted with dichloromethane (10 mL). The dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to give another portion of product as a light yellow oil which solidified upon cooling in the refrigerator (0.053 g, 0.299 g total, 81% yield).1 H NMR (400MHz, C6D6): δ6.98 (s, 2H), 0.91 (s, 9H).

[0151] 2',2"'-(4-tert-butyl)-thiopyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) To 4-(tert-butyl)-thioxo-2,6-dichloropyridine (0.150 g, 0.635 mmol), 4-((1s,3s)-adamantan-1-yl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.544 g, 1.27 mmol, 2 equiv), chloro(2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (20 mg, 26 μmol, 4 mol%) and cesium carbonate (1.24 g, 3.81 mmol, 6 equiv) in 1,4-dichloropyridine was added a mixture of ... Degassed water (3 mL) was added to the stirred solution in pentane (6 mL). The reactants were stirred and heated to reflux for 5 hours under nitrogen. The reactants were cooled to room temperature. The reactants were poured into a beaker and the contents of the flask were washed into the beaker with water (50 mL) and dichloromethane (50 mL). The contents of the beaker were poured into a separatory funnel, shaken, and the organic layer was extracted. The aqueous phase was further extracted with additional dichloromethane (2×20 mL). The combined organic extracts were washed with water, dried over anhydrous sodium sulfate, and filtered on a short silica pad. The filtrate was concentrated in vacuo. The residue was stirred in pentane (2 mL) for 30 minutes, during which a white solid was precipitated. The suspension was filtered, the white solid was collected and concentrated under high vacuum to give the product as a white solid (0.504 g, 89% yield, mixture of diastereomers). 1 H NMR (400 MHz, C6D6), diastereoisomers integrated into one: δ 7.94 (s, 1H), 7.38-7.18 (m, 10H), 6.81 and 6.47 (d, J = 2.3 Hz, and s, respectively, total 3H), 2.44-1.72 (m, 30H), 1.30-0.97 (27H).

[0152] 4-(Butylthio)-2,6-dichloropyridine To a precooled, stirred solution of 2,6-dichloro-4-nitropyridine (0.300 g, 1.55 mmol) in tetrahydrofuran (4 mL) was added a solution of sodium butanethiolate (0.209 g, 95% pure, 1.8 mmol, 1.1 equiv) in tetrahydrofuran (4 mL). The reaction was stirred at room temperature for 1 hour. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (10 mL, then 5 mL) and filtered on Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to give the product as a yellow oil (276 mg, 75% yield). 1 H NMR (400MHz, C6D6): δ6.53 (s, 2H), 2.05 (t, 2H, J = 7.2Hz), 1.17-1.07 (m, 2H), 1.07-0.96 (m, 2H), 0.65 (t, 3H, J = 7.2Hz).

[0153] 2',2"'-(4-(Butylthio)-pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) To 4-(Butylthio)-2,6-dichloropyridine (81 mg, 0.34 mmol), 4-((1s,3s)-adamantan-1-yl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (294 mg, 0.69 mmol, 2 equiv), cesium carbonate (671 mg, 2.06 mmol, 6 equiv) and chloro(2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (11 mg, 14 μmol, 4 mol%) in dichloromethane was added. Deaerated water (2.5mL) is added to the stirred mixture in alkane (5mL). The reactant is stirred and heated to 100 ℃ and kept for 5 hours. The reactant is cooled to room temperature. The reactant is distributed between dichloromethane (40mL) and water (50mL) in a separatory funnel. The organic extract is collected, and the aqueous phase is further extracted with additional dichloromethane (20mL). The combined dichloromethane extracts are washed with water (50mL), dried over anhydrous magnesium sulfate and filtered. The filtrate is concentrated in a vacuum. The crude solid is purified by silica gel column chromatography to obtain product (311mg, quantitative yield, a mixture of two diastereomers). 1H NMR (400 MHz, C6D6), diastereoisomers integrated into one: δ 8.25 (s, 2H), 7.39-7.23 (m, 6H), 7.15-7.08 (m, 3H), 6.85-6.68 (m, 3H), 2.48-1.76 (m, 32H), 1.46-1.11 (m, 22H), 0.74 (t, 3H, J = 7.3 Hz).

[0154] Lithium dodecanethiol To a precooled, stirred solution of dodecanethiol (1.0 mL, 4.2 mmol) in diethyl ether (10 mL) was added n-butyllithium (1.6 mL, 2.71 M in hexanes, 4.3 mmol, 1 equiv.) dropwise. The reaction was stirred at room temperature for 105 minutes. The reaction was filtered on a plastic sintered funnel. The filtered solid was hexanes (2 x 5 mL), collected and concentrated under high vacuum to give the product as a white solid (557 mg, 64% yield). 1 H NMR (400MHz, C4D8O): δ2.38 (t, 2H, J = 7.3Hz), 1.53-1.42 (m, 2H), 1.42-1.33 (m, 2H), 1.33-1.20 (m, 16H), 0.89 (t, 3H, J = 6.6Hz).

[0155] 2,6-Dichloro-4-dodecylthiopyridine To a precooled, stirred solution of 2,6-dichloro-4-nitropyridine (200 mg, 1.04 mmol) in tetrahydrofuran (10 mL) was added lithium dodecanethiol (218 mg, 1.05 mmol, 1 equiv) and additional tetrahydrofuran (5 mL). The reaction was stirred at room temperature for 16.5 hours. The reaction was then concentrated under a stream of nitrogen and under high vacuum. The residue was stirred in pentane (10 mL). The resulting yellow suspension was filtered on a plastic sinter funnel and further extracted with additional pentane (10 mL). The combined pentane extracts were then concentrated under a stream of nitrogen and under high vacuum. The crude product was purified by silica gel column chromatography to give the product as an orange-red oil (143 mg, 39% yield). 1 H NMR (400MHz, C6D6): δ6.57 (s, 2H), 2.12 (t, 2H, J = 7.3Hz), 1.40-1.14 (m, 16H), 1.13-1.04 (m, 4H), 0.92 (t, 3H, J = 7.0Hz).

[0156] 2',2"'-(4-(Dodecylthio)-pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) 2,6-Dichloro-4-(dodecylthio)pyridine (76 mg, 0.22 mmol), 4-((1s,3s)-adamantan-1-yl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (187 mg, 0.436 mmol, 2 equiv), cesium carbonate (426 mg, 1.31 mmol, 6 equiv) and chloro(2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (7 mg, 9 μmol, 4 mol%) in dichloro-4-(dodecylthio)pyridine (76 mg, 0.22 mmol), 4-((1s,3s)-adamantan-1-yl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (187 mg, 0.436 mmol, 2 equiv), cesium carbonate (426 mg, 1.31 mmol, 6 equiv) and chloro(2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (7 mg, 9 μmol, 4 mol%) were added in dichloro-4-(dodecylthio)pyridine (76 mg, 0.22 mmol), 4-((1s,3s)-adamantan-1-yl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (187 mg, 0.436 mmol, 2 equi Deaerated water (2mL) is added to the stirred mixture in pentane (4mL). The reactant is stirred and heated to 100°C for 19.5 hours. The reactant is cooled to room temperature. The reactant is distributed between dichloromethane and water. The organic layer is collected, and the aqueous phase is extracted once more with dichloromethane. The combined dichloromethane extracts are dried over anhydrous sodium sulfate and filtered. The filtrate is concentrated in vacuo. The foam obtained is stirred in pentane. The solution is then concentrated in vacuo to obtain the product, which is an amber foam (179mg, 82% yield). 1 H NMR (400 MHz, C6D6), diastereoisomers integrated into one: δ 8.22 (s, 1H), 7.44-7.17 (m, 8H), 7.13-6.73 (m, 5H), 2.44-1.73 (m, 32H), 1.50-1.07 (m, 38H), 0.87 (t, 3H, J = 7.1 Hz).

[0157] 4-(4-(tert-Butyl)phenyl)-2,6-dichloropyridine To a solution of 1-bromo-4-tert-butyl-benzene (2.00 g, 9.38 mmol) in diethyl ether (50 mL) was added dropwise 5.86 mL of 1.6 M 2-naphthalene in hexanes at ambient temperature. n BuLi (9.38mmol). The reaction mixture was stirred at this temperature for 30 minutes. All volatiles were then removed under vacuum. The intermediate was isolated as a white solid (1.13g, 8.03mmol), which was then mixed with anhydrous ZnCl2 (1.09g, 8.03mmol) in THF (10mL). The mixture was stirred for 10 minutes, and then 2,6-dichloro-4-iodo-pyridine (2.00g, 7.3mmol) was added. The mixture was then cooled to -20°C. Pd (Pt After the addition of 4-nitro-1-yl pyrrolidone (4-nitro-1-yl)-2-nitropropene (4-nitro-1-yl)-2-nitropropene (5-nitro-1-yl)-2-nitropropene (5-nitro-1-yl)-2-nitropropene (5-nitro-1-yl)-2-nitropropene (5-nitro-1-yl)-2-nitropropene (5-nitro-1-yl)-2-nitropropene (5-nitro-1-yl)-2-nitropropene (5-nitro-1-yl)-2-nitropropene (5-nitro-1-yl)-2-nitropropene (5-nitro-1-yl)-2-nitropropene (5-nitro-1-yl)-2-nitropropene (5-nitro-1-yl)-2-nitropropene ( 1 H NMR (400MHz, CDCl3) δ7.53(s,4H),7.46(s,2H),1.36(s,9H).

[0158] 2',2"'-(4-(4-(tert-butyl)phenyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.584 g, 1.36 mmol) was added to 1,4-dihydro- 4-(4-(tert-butyl)phenyl)-2,6-dichloropyridine (0.191 g, 0.68 mmol), cesium carbonate (1.33 g, 4.09 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 20.0 mg, 0.03 mmol) and water (3 mL) were added to a solution in 2,4-dichloro-1,6-dichloropyridine (6 mL). The reaction mixture was stirred at 100 °C for 15 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with dichloromethane (20 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The crude product was stirred in methanol until the pure product precipitated as a white solid and then isolated by filtration to give the product (0.573 g, 91%) as a mixture of two isomers. 1H NMR (400 MHz, CDCl3) δ 8.05 (s, 2H in A), 7.72-7.63 (m, 2H in A), 7.59-7.38 (m, 6H), 7.34 (d, J = 8.2 Hz, 2H), 7.18 (s, 2H in B), 7.14 (s, 2H in A), 7.06 (s, 2H), 6.99 (d, J = 8.1 Hz, 2H in A), 6.94 (s, 1H in B), 6.92 (s, 1H in B), 6.59 (s, 2H in A), 6.36 (s, 1H in B), 2.16-1.83 (m, 18H), 1.67 (br, 12H), 1.32 (s, 9H), 1.17 (s, 18H in B), 0.97 (s, 18H in A).

[0159] 2,6-Dibromoisonicotinic acid Citrazinic acid (3.0 g, 19.3 mmol) and phosphorus oxybromide (16.3 g, 58.0 mmol) were combined in a sealed round bottom flask and heated at 150°C for 2 hours. Once cooled, water was added and the mixture was stirred overnight. The suspension was extracted three times with ethyl acetate and the combined organic fractions were dried (MgSO4), filtered and concentrated to give the product as a brown solid in 83% yield. 1 H NMR (500MHz, CDCl3, δ): 8.06 (s, 2H).

[0160] (2,6-Dibromopyridin-4-yl)methanol 2,6-Dibromoisonicotinic acid (1.1 g, 4.0 mmol) was dissolved in 15 mL THF and cooled to 0 °C. Borane-THF (10.1 mL, 1.0 M in THF) was slowly added and the reaction was stirred overnight at ambient temperature. The reaction was quenched with water, adjusted to alkalinity with saturated sodium bicarbonate, and extracted with dichloromethane. The organic solution was dried (MgSO4), filtered and concentrated to give the product as a white solid in 69% yield. 1 H NMR (500MHz, CDCl3, δ): 4.29 (s, 2H), 7.47 (s, 2H).

[0161] 4-(Bromomethyl)-2,6-dibromopyridine Dissolve (2,6-dibromopyridin-4-yl)methanol (3.3 g, 12.3 mmol) in 200 mL of dibromopyridin-4-yl Phosphorus tribromide (2.2 mL, 13.6 mmol) was added and the reaction was heated at 40 °C for 30 minutes and then at ambient temperature overnight. The reaction was quenched with saturated sodium bicarbonate and concentrated to remove dihydrogen sulfoxide. The solution was extracted with dichloromethane, dried over MgSO4, filtered and concentrated to a white solid. 1 H NMR (500MHz, CDCl3, δ): 4.29 (s, 2H), 7.47 (s, 2H).

[0162] 4-(N,N-diisopropylaminomethyl)-2,6-dibromopyridine 4-(Bromomethyl)-2,6-dibromopyridine (343 mg, 1.0 mmol) and diisopropylamine (0.41 mL, 0.31 mmol) were dissolved in 5 mL of acetonitrile and heated at 60°C overnight. The mixture was filtered and concentrated under reduced pressure. The pure product was obtained as a pale yellow solid by recrystallization in isohexane in 82% yield. 1 H NMR (500MHz, CDCl3, δ): 1.01 (d, J=7.0Hz, 12H), 2.99 (m, 2H), 3.58 (s, 2H), 7.48 (s, 2H).

[0163] 2',2"'-(4-(N,N-diisopropylaminomethyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.142 g, 0.33 mmol) was added to 1,4-dihydro- 4-(N,N-diisopropylaminomethyl)-2,6-dibromopyridine (0.058 g, 0.17 mmol), cesium carbonate (0.324 g, 1.00 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 4.8 mg, 0.007 mmol) and water (2 mL) were added to a solution in 2% ethanol (4 mL). The reaction mixture was stirred at 100 ° C for 15 hours, then cooled to ambient temperature and diluted with water (2 mL). The resulting mixture was diluted with dichloromethane (10 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×5 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The crude product was stirred in methanol until the pure product precipitated as a white solid, which was then isolated by filtration to give the product (0.121 g, 80%) as a mixture of two isomers. 1 H NMR (400 MHz, CDCl3) δ 8.29 (s, 2H in A), 7.54-7.32 (m, 8H), 7.12 (s, 2H in B), 7.10-6.95 (m, 4H), 6.69 (s, 2H in B), 6.55 (d, J = 2.4 Hz, 2H in A), 3.45-3.25 (m, 2H), 2.89 (tt, J = 13.1, 6.5 Hz, 2H), 2.04-1.73 (m, 18H), 1.61 (br, 12H), 1.15 (s, 18H in B), 1.00 (s, 18H in A), 0.91 (q, J = 6.5, 6.1 Hz, 12H).

[0164] 2,6-Dibromo-4-(4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl)pyridine 2,6-dibromoisonicotinic acid (886mg, 3.1mmol), (3-methyloxetane-3-yl)methanol (0.31mL, 3.1mmol) and dimethylaminopyridine (38mg, 0.31mmol) were dissolved in 10mL dichloromethane. Dicyclohexylcarbodiimide (715mg, 3.4mmol) in 2ml dichloromethane was added dropwise. After the reaction was determined to be complete by TLC, the mixture was filtered and the filtrate was washed with 10% HCl, saturated sodium bicarbonate and water. It was then dried (MgSO4), filtered and concentrated. The crude oxetane ester (513mg, 1.4mmol) was redissolved in dichloromethane and cooled to -70°C. Borane trifluoride diethyl etherate (0.34mL, 0.28mmol) was added and the reactants were stirred overnight. It was quenched with triethylamine (0.77 mL, 0.56 mmol), concentrated, redissolved in ether, then washed with water, dried over MgSO4, filtered, and concentrated to a yellow solid. The product was obtained in 59% yield. 1 HNMR (500MHz, CDCl3, δ): 0.89 (s, 3H), 4.06 (s, 6H), 7.66 (s, 2H).

[0165] 2',2"'-(4-(4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.236 g, 0.55 mmol) was added to 1,4-dihydro- 2,6-bromo-4-(4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)pyridine (0.100 g, 0.27 mmol), cesium carbonate (0.538 g, 1.64 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 8.0 mg, 0.01 mmol) and water (2 mL) were added to a solution in 2% ethanol (4 mL). The reaction mixture was stirred at 100 ° C for 15 hours, then cooled to ambient temperature and diluted with water (2 mL). The resulting mixture was diluted with dichloromethane (10 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×5 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The crude product was stirred in methanol until the pure product precipitated as a white solid which was then isolated by filtration to afford the product (0.211 g, 83%) as a mixture of two isomers.1 H NMR (400 MHz, CDCl3) δ 8.18 (s, 2H in A), 7.59-7.37 (m, 8H), 7.33 (s, 2H in B), 7.31 (d, J = 2.4 Hz, 2H in B), 7.22 (s, 2H in A), 7.09 (br, 2H), 6.61 (d, J = 8.4 Hz, 2H in B), 6.50 (s, 2H in A), 2.16-1.79 (m, 18H), 1.68 (s, 12H), 1.15 (s, 18H in B), 1.02 (s, 18H in A), 0.86 (s, 3H).

[0166] 2,6-Dibromo-4-((p-tolyloxy)methyl)pyridine 4-(Bromomethyl)-2,6-dibromopyridine (300 gm, 0.9 mmol), p-cresol (108 mg, 1.0 mmol) and cesium carbonate (595 mg, 1.8 mmol) were combined in 5 mL of acetonitrile and heated at 60°C. After 1 hour the mixture turned dark blue, but TLC indicated that the reaction was incomplete. Additional portions of p-cresol were added and the reaction was stirred at ambient temperature over the weekend. The mixture was filtered and concentrated under reduced pressure. The product was purified by silica gel chromatography (10% acetone / isohexane). 1 H NMR (500MHz, CDCl3, δ): 2.37 (s, 3H), 5.00 (s, 2H), 6.81 (m, 2H), 7.11 (m, 2H), 7.53 (s, 2H).

[0167] 2',2"'-(4-((p-tolyloxy)methyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.236 g, 1.18 mmol) was added to 1,4-dihydro- 2,6-dibromo-4-((p-tolyloxy)methyl)pyridine (0.211 g, 0.59 mmol), cesium carbonate (1.16 g, 3.55 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 8.6 mg, 0.01 mmol) and water (2 mL) were added to a solution in 2% paraformaldehyde (4 mL). The reaction mixture was stirred at 100 ° C for 15 hours, then cooled to ambient temperature and diluted with water (2 mL). The resulting mixture was diluted with dichloromethane (10 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×5 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The crude product was stirred in methanol until the pure product precipitated as a white solid and then isolated by filtration to give the product (0.497 g, 92%) as a mixture of three isomers. 1 H NMR (400 MHz, CDCl3) δ 8.20 (dd, J = 14.7, 8.1 Hz, 2H in C), 8.06 (s, 2H in A), 7.66 (dd, J = 6.1, 3.0 Hz, 8H in C), 7.58-7.31 (m, 8H in A and B), 7.18 (d, J = 2.5 Hz, 2H in B), 7.14 (d, J = 8.2 Hz, 4H in B), 7.11-7.02 (m, 4H in A), 7.00 (s, 2H in A), 6.96 (d, J = 8.5 Hz, 4H in C), 6.91 (d, J = 2.4 Hz, 2H in B ), 6.88(d, J=2.4Hz, 2H in C), 6.75-6.69(m, 2H in A), 6.67(s, 2H in B), 6.64(s, 2H in C), 6.53(d, J=2.3Hz, 2H in A), 6.50(s, 2H in B), 6.43(s, 2H in C), 4.80-4.62(m, 2H), 2.28(s, 3H), 2.19-1.76(m, 18H), 1.77-1.60(m, 12H), 1.22(s, 18H in C), 1.14(s, 18H in B), 1.00(s, 18H in C).

[0168] 2,6-Dichloro-4-(n-butyldimethylsilyl)pyridine A solution of isopropylmagnesium chloride lithium chloride complex in THF (1.3M, 2.95mL, 3.83mmol) and a solution of 2,6-dichloro-4-iodopyridine (1.00g, 3.65mmol) in THF (5mL) were cooled in a cooling bath at -40°C for 10 minutes. The cooled solution of isopropylmagnesium chloride lithium chloride complex was then slowly added to the 2,6-dichloro-4-iodopyridine solution and then stirred at -40°C for 15 minutes. Then n-butyldimethylsilyl chloride (0.550g, 3.65mmol) was added. The reaction mixture was stirred at -40°C for 20 minutes and then stirred at ambient temperature for 16 hours. The reactants were quenched with water (5mL). The resulting mixture was diluted with hexane (10mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10mL). The combined organic extracts were dried over MgSO4 and then concentrated. The crude product was filtered on a silica pad. After removal of the solvent, the pure product was isolated as a clear oil (0.780 g, 81%). 1 H NMR (400MHz, CDCl3) δ7.29 (s, 2H), 1.41-1.18 (m, 4H), 0.87 (t, J = 7.1Hz, 3H), 0.81-0.69 (m, 2H), 0.28 (s, 6H).

[0169] 2',2"'-(4-(n-butyldimethylsilyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.653 g, 1.53 mmol) was added to 1,4-dihydro- 2,6-dichloro-4-(n-butyldimethylsilyl)pyridine (0.200 g, 0.76 mmol), cesium carbonate (1.49 g, 4.58 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 22.0 mg, 0.03 mmol) and water (3 mL) were added to a solution in 2,6-dichloro-4-(n-butyldimethylsilyl)pyridine (0.200 g, 0.76 mmol), cesium carbonate (1.49 g, 4.58 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 22.0 mg, 0.03 mmol) and water (3 mL). The reaction mixture was stirred at 100 ° C for 5 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with dichloromethane (20 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The crude product was dissolved in ethanol at 80 ° C. The resulting solution was then stored at -20 °C for 2 hours and then filtered to give the product (0.64 g, 92%) as a mixture of two isomers. 1 H NMR (400 MHz, CDCl3) δ 8.09 (s, 2H in A), 7.60-7.34 (m, 8H), 7.11 (s, 2H in B), 7.07 (s, 2H in A), 7.01 (s, 2H), 6.92 (s, 2H in B), 6.55 (s, 2H in A), 6.41 (s, 2H in B), 2.11-1.79 (m, 18H), 1.65 (br, 12H), 1.38-1.21 (m, 4H), 1.17 (s, 18H in B), 0.98 (s, 18H in A), 0.84 (t, J = 7.5 Hz, 3H), 0.50 (d, J = 9.0 Hz, 2H), 0.01 (s, 6H in B), -0.03 (s, 6H in A).

[0170] Lithium (1R,2S,5R)-2-isopropyl-5-methyl-cyclohexane-1-ol) To a precooled, stirred solution of L-menthol (1.057 g, 6.76 mmol) in diethyl ether (50 mL) was added n-butyl lithium (4.2 mL, 1.64 M in hexanes, 6.9 mmol, 1 equiv). The reaction was stirred at room temperature for 3 hours. The reaction was concentrated under a stream of nitrogen and then under high vacuum to give the product as a white solid (1.117 g, quantitative yield). 1H NMR (400MHz, C4D8O): δ3.27(td,1H,J=9.7,4.0Hz), 2.33(pd,1H,J=6.9,2.3Hz), 1.89(dtd,1H,J=12.2,3.6,2.2Hz), 1.62(dt,1H,J=12.4,3.1Hz),1.50(dq,1H,J=12.6,3.2Hz),1.45-1.25(m,1H),1.00-0.84(m,7H),0.84-0.71(m,6H).

[0171] 2,6-Dichloro-4-(((1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl)oxy)pyridine To a precooled, stirred solution of 2,6-dichloro-4-nitropyridine (433 mg, 2.24 mmol, 1 equiv.) in tetrahydrofuran was added [(1R, 2S, 5R) -2-isopropyl-5-methyl-cyclohexane-1-ol] lithium (364 mg, 2.24 mmol). The reaction was stirred at room temperature for 3 hours. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in pentane (15 mL). The resulting suspension was filtered over celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give the product as a yellow oil (566 mg, 83% yield). 1 H NMR (400MHz, C6D6): δ6.53 (s, 2H), 3.62 (td, 1H, J = 10.6, 4.3Hz), 1.91 (heptd, 1H, J = 7.0, 2.8Hz), 1.68 (dtd, 1H, J = 12.3, 3.7, 1 .8Hz),1.44-1.34(m,2H),1.31-1.17(m,1H),0.98-0.85(m,1H),0.79(d,3H,J=7.1Hz),0.75-0.65(m,5H),0.62-0.54(m,4H).

[0172] 2',2"'-((4-(((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)oxy)pyridine)-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-phenol) To 2,6-dichloro-4-(((1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl)oxy)pyridine (148 mg, 0.490 mmol), 4-((1s,3s)-adamantan-1-yl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (420 mg, 0.979 mmol, 2 eq), cesium carbonate (957 mg, 2.94 mmol, 6 eq) and chloro(2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (15 mg, 19 μmol, 4 mol%) in dichloro-4-(((1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl)oxy)pyridine (148 mg, 0.490 mmol), 4-((1s,3s)-adamantan-1-yl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (420 mg, 0.979 mmol, 2 eq), cesium carbonate (957 mg, 2.94 mmol, 6 eq) and chloro(2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (15 mg, 19 μmol, 4 mol%) were added. Degassed water (2.5 mL) was added to the stirred mixture in pentane (5 mL). The reactants were stirred and heated to 100 ° C for 4.5 hours. The reactants were cooled to room temperature. The reactants were distributed between dichloromethane (50 mL) and water (50 mL) in a separatory funnel. The organic phase was collected and the aqueous phase was further extracted with additional dichloromethane (20 mL). The combined organic phases were filtered on a thin pad of silica. The filtrate was concentrated in vacuo. The crude product was stirred with pentane (5 mL), and the resulting solution was concentrated under a stream of nitrogen, and then concentrated under high vacuum to obtain the product (441 mg, 94% yield, a mixture of diastereomers). 1 H NMR (400 MHz, C6D6), diastereoisomers integrated into one: δ 8.69-8.53 (m, 1H), 7.47-7.19 (m, 7H), 7.14-7.08 (m, 3H), 6.86-6.53 (m, 3H), 3.92-3.70 (m, 1H), 2.44-1.72 (m, 31H), 1.58-0.96 (m, 24H), 0.95-0.58 (11H).

[0173] 2',2"'-(4-ethoxypyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) To a stirred solution of 2,6-dichloro-4-ethoxy-pyridine (50 mg, 0.26 mmol), 4-((1s,3s)-adamantan-1-yl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (223 mg, 0.521 mmol, 2 equiv), cesium carbonate (509 mg, 1.56 mmol, 6 equiv) and chloro(2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (8 mg, 10 μmol, 4 mol%) in 1,4-dichloro-4-ethoxy-pyridine was added a precipitate of 1% paraffin and 1% paraffin. Deaerated water (2mL) is added to the mixture in alkane (4mL). The reactant is stirred and heated to 100 ℃ for 6 hours. The reactant is cooled to room temperature. The reactant is distributed between dichloromethane (50mL) and water (50mL) in a separatory funnel. The organic extract is collected, and the aqueous phase is further extracted with additional dichloromethane (20mL). The combined organic extracts are filtered on a thin pad of silica. The filtrate is concentrated in vacuo. The residue is stirred in pentane (5mL). The resulting solution is then concentrated under a stream of nitrogen, and then concentrated under high vacuum to obtain the product, which is a white solid (128mg, 58% yield, a mixture of diastereomers). 1 H NMR (400 MHz, C6D6), diastereoisomers integrated into one: δ8.40 (s, 2H), 7.45-7.10 (m, 8H), 6.81 (d, 2H, J = 2.4 Hz), 6.41 (s, 2H), 3.34-3.10 (m, 2H), 2.32-1.97 (m, 18H), 1.88-1.73 (m, 12H), 1.29 / 1.14 (two peaks, 18H), 0.95 (t, 3H, J = 7.0 Hz).

[0174] 2,6-Dichloro-3-(n-butyldimethylsilyl)pyridine A solution of isopropylmagnesium chloride lithium chloride complex in THF (1.3M, 2.84mL, 3.70mmol) and a solution of 2,6-dichloro-3-iodopyridine (0.964g, 3.52mmol) in THF (5mL) were cooled in a cooling bath at -40°C for 10 minutes. The cooled solution of isopropylmagnesium chloride lithium chloride complex was then slowly added to the 2,6-dichloro-3-iodopyridine solution and then stirred at -40°C for 15 minutes. Then n-butyldimethylsilyl chloride (0.530g, 3.52mmol) was added. The reaction mixture was stirred at -40°C for 20 minutes and then stirred at ambient temperature for 16 hours. The reactants were quenched with water (5mL). The resulting mixture was diluted with hexane (10mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10mL). The combined organic extracts were dried over MgSO4 and then concentrated. The crude product was filtered on a silica pad. After removal of the solvent, the pure product was isolated as a clear oil (0.910 g, 98%). 1 H NMR (400MHz, CDCl3) δ7.68 (d, J = 7.7Hz, 1H), 7.23 (d, J = 7.7Hz, 1H), 1.39-1.15 (m, 4H), 0.95-0.80 (m, 5H), 0.35 (s, 6H).

[0175] 2',2"'-(4-(n-butyldimethylsilyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.653 g, 1.53 mmol) was added to 1,4-dihydro- 2,6-dichloro-3-(n-butyldimethylsilyl)pyridine (0.200 g, 0.76 mmol), cesium carbonate (1.49 g, 4.58 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 22.0 mg, 0.03 mmol) and water (3 mL) were added to a solution in 2,6-dichloro-3-(n-butyldimethylsilyl)pyridine (0.200 g, 0.76 mmol), cesium carbonate (1.49 g, 4.58 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 22.0 mg, 0.03 mmol) and water (3 mL). The reaction mixture was stirred at 100 ° C for 5 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with dichloromethane (20 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The crude product was dissolved in ethanol at 80 ° C. The resulting solution was then stored at -20 °C for 2 hours and then filtered to give the product (0.64 g, 92%) as a mixture of two isomers. 1 H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 8.3 Hz, 1H in B), 8.05 (d, J = 2.4 Hz, 1H in A), 7.76-7.31 (m, 8H), 7.31-7.22 (m, 1H), 7.18 (d, J = 7.9 Hz, 1H), 7.10 (d, J = 2.5 Hz, 1H) Hz, 1H), 6.72(d, J=2.4Hz, 1H), 6.12(d, J=6.7Hz, 2H), 2.43-1.58(m, 30H), 1.41(s, 18H in B), 1.39-1.19(m, 4H), 1.12(s, 18H in A), 0.84(t, J=7.2Hz, 3H), 0.66-0.43(m, 2H), -0.01(d, J=8.4Hz, 6H).

[0176] 2,6-Dichloro-4-(hept-1-yn-1-yl)pyridine 1-Heptyne (0.372 g, 3.87 mmol), diisopropylamine (1.85 g, 18.3 mmol), CuI (0.07 g, 0.37 mmol) and PdCl2(PPh3)2 (0.13 g, 0.18 mmol) were added sequentially to a stirred solution of 2,6-dichloro-4-iodopyridine (1.00 g, 3.65 mmol) in degassed THF (20 mL). The reaction mixture was stirred at room temperature for 12 hours. The reactant was then quenched with water (1 mL), and the organic phase was filtered through Celite. The product was purified by flash chromatography on silica gel (hexane / DCM 9:1) to give a yellow oil (0.74 g, 84%). 1 H NMR (400MHz, CDCl3) 7.21 (s, 2H), 2.42 (t, J = 7.1Hz, 2H), 1.66-1.52 (m, 2H), 1.47-1.25 (m, 4H), 0.92 (t, J = 7.1Hz, 3H).

[0177] 2',2"'-(4-(hept-1-yn-1-yl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.743 g, 1.73 mmol) was added to 1,4-dihydro- 2,6-dichloro-4-(hept-1-yn-1-yl)pyridine (0.210 g, 0.86 mmol), cesium carbonate (1.70 g, 5.20 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 12.0 mg, 0.02 mmol) and water (3 mL) were added to a solution in 2,6-dichloro-4-(hept-1-yn-1-yl)pyridine (0.210 g, 0.86 mmol), cesium carbonate (1.70 g, 5.20 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 12.0 mg, 0.02 mmol) and water (3 mL). The reaction mixture was stirred at 100 ° C for 15 hours, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with dichloromethane (20 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×10 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The crude product was passed through silica gel eluted with 20% dichloromethane in hexane to give the product (0.43 g, 56%) as a mixture of two isomers. 1H NMR (400 MHz, CDCl3) δ 8.03 (s, 2H in A), 7.59-7.31 (m, 8H), 7.12 (d, J = 2.4 Hz, 2H), 7.00 (s, 2H in B), 6.92 (s, 2H), 6.56 (d, J = 2.3 Hz, 2H), 2.35 (t, J = 7.0 Hz, 2H), 2.09-1.82 (m, 18H), 1.70 (d, J = 4.3 Hz, 12H), 1.59-1.52 (m, 2H), 1.44-1.25 (m, 4H), 1.19 (s, 18H in B), 1.05 (s, 18H in A), 0.92 (t, J = 6.8 Hz, 3H).

[0178] 2,6-Dichloroisonicotinic acid In a thick-walled round-bottom flask, citrazinic acid (10.3 g, 66.7 mmol) and triethylammonium chloride (11.0 g, 66.7 mmol) were dissolved in 20 mL of phosphorus oxychloride. The flask was sealed and heated at 100 ° C overnight. Once cooled, the mixture was poured onto ice and extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried (MgSO4), filtered and concentrated to give a pink solid in 81% yield. The product was obtained in 69% yield using 0.1 equivalents of triethylammonium chloride. 1 H NMR (500MHz, CDCl3, δ): 7.87 (s, 2H).

[0179] (2,6-Dichloropyridin-4-yl)methanol 2,6-Dichloroisonicotinic acid (8.94 g, 46.5 mmol) was dissolved in 50 mL THF and cooled to 0°C. Borane-THF (116 mL, 1.0 M in THF) was slowly added and the reaction was stirred overnight at ambient temperature. The reaction was quenched with water, adjusted to alkalinity with saturated sodium bicarbonate, and extracted with dichloromethane. The organic solution was dried (MgSO4), filtered and concentrated to give the product as a white solid in 91% yield.

[0180] 2,6-Dichloroisonicotinaldehyde (2,6-Dichloropyridin-4-yl)methanol (540 mg, 3.0 mmol) was dissolved in 5 mL of dichloromethane. Dess-Martin periodinane (1.5 g, 3.6 mmol) was added and the reaction was stirred at ambient temperature for 3 hours. The mixture was concentrated and then purified by silica gel column chromatography (30% acetone / isohexane) to give the aldehyde in 70% yield. 1H NMR (500MHz, CDCl3, δ): 7.67 (s, 2H), 10.00 (s, 1H).

[0181] 8-(2,6-Dichloropyridin-4-yl)-1,5-diazabicyclo[3.2.1]octane 2,6-Dichloroisonicotinaldehyde (240 mg, 1.3 mmol) and 1,4-diazepane (136 mg, 1.3 mmol) were dissolved in 10 mL of ethanol and stirred overnight at ambient temperature. The solution was concentrated to an oil and then purified by column chromatography (30% acetone / isohexane). The product was obtained as a white solid with a yield of 57%. Rf = 0.29 (30:70 acetone / isohexane); 1 13C NMR:18.4,49.9(2C),55.8(2C),86.8,120.9(2C),150.7(2C),154.9.

[0182] Predictive Synthesis of 2',2"'-(4-(1,5-diazabicyclo[3.2.1]octan-8-yl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) Then 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (0.236 g, 0.55 mmol) was added to 1,4-dihydro- 8-(2,6-dichloropyridin-4-yl)-1,5-diazabicyclo[3.2.1]octane (0.070 g, 0.27 mmol), cesium carbonate (0.538 g, 1.64 mmol), Buchwald RuPhos Palladacycle Gen II precatalyst (Strem, CAS1375325-68-0, 8.0 mg, 0.01 mmol) and water (2 mL) were added to a solution in 2,4-dichloropyridin-4-yl)-1,5-diazabicyclo[3.2.1]octane (4 mL). The reaction mixture was stirred at 100 ° C for 15 hours, then cooled to ambient temperature and diluted with water (2 mL). The resulting mixture was diluted with dichloromethane (10 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2×5 mL). The combined organic extracts were dried over MgSO4 and then concentrated to dryness. The crude product was stirred in methanol until the pure product precipitated as a white solid, which was then filtered to obtain the product.

[0183] 1,3,5-Trimethyladamantane In a Parr pressure reactor, 22.3 mL (64.0 mmol) of 2.9 M MeMgBr in diethyl ether was added in one portion to a solution of 15.0 g (62.0 mmol) of 1-bromo-3,5-dimethyladamantane in 80 mL of diethyl ether. The resulting solution was heated to 105°C and stirred at this temperature overnight. Afterwards, the reactor was cooled to room temperature and the pressure was released. Another 100 ml of 10% HCl was carefully added. The resulting mixture was extracted with diethyl ether (3×30 mL), and the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. 11.3 g (99%) of a colorless oil was produced. 1 H NMR (CDCl3, 400MHz): δ1.98-2.03(m,1H), 1.25-1.28(m,6H), 1.00-1.12(m,6H), 0.78(s,9H). 13 C NMR (CDCl3, 100MHz) δ51.1, 43.2, 31.4, 30.7, 30.0.

[0184] 3,5,7-Trimethyladamantan-1-ol Then, 103 ml of water, 70 ml of carbon tetrachloride, 55.0 g (255 mmol) of sodium periodate and 330 mg (1.28 mmol) of RuCl3(H2O) were added to a solution of 11.3 g (62.0 mmol) of 1,3,5-trimethyladamantane in 70 ml of acetonitrile. xThe resulting suspension was stirred at 60°C for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The resulting mixture was extracted with dichloromethane (3×50 ml), the combined organic extracts were dried over Na2SO4 and evaporated to dryness. The residue was purified using a Kugelrohr apparatus (1 mbar, 100°C). 12.1 g (96%) of a white crystalline solid was obtained. 1 H NMR (CDCl3, 400MHz): δ1.44 (br.s, 1H), 1.30 (s, 6H), 0.97-1.15 (m, 6H), 0.88 (s, 9H). 13 C NMR (CDCl3, 100MHz) δ70.5, 50.7, 49.8, 34.1, 29.5.

[0185] 4-Methyl-2-(3,5,7-trimethyladamantan-1-yl)phenol To a solution of 20.8 g (192 mmol) 4-methylphenol and 18.7 g (96.3 mmol) 3,5,7-trimethyladamantan-1-ol in 100 mL dichloromethane was added dropwise 5.8 ml sulfuric acid (96%) for 30 minutes at room temperature. The resulting mixture was stirred at room temperature for 30 minutes and then carefully poured into 300 ml of 3% ammonia. The crude product was extracted with dichloromethane (3 x 50 ml), and the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residue was purified using a Kugelrohr apparatus (0.3 mbar, 160°C) to give 23.1 g (84%) of the title product as a white crystalline solid. 1 H NMR (CDCl3, 400MHz): δ7.04 (d, J=2.1Hz, 1H), 6.86 (ddd, J=7.9, 2.2, 0.6Hz, 1H), 6.55 (d, J=7.9Hz), 4.52 (s, 1H), 2.29 (s, 3H), 1.67 (s, 6H), 1.10-1.18 (m, 6H), 0.90 (s, 9H). 13 CNMR (CDCl3, 100MHz): δ151.9,135.2,129.7,127.7,127.0,116.6,50.4,46.1,39.1,32.1,30.6,20.9.

[0186] 2-Bromo-4-methyl-6-(3,5,7-trimethyladamantan-1-yl)phenol To a solution of 8.97 g (31.5 mmol) of 4-methyl-2-(3,5,7-trimethyladamantan-1-yl)phenol in 90 mL of dichloromethane was added dropwise 5.04 g (31.5 mmol) of bromine at room temperature. The resulting mixture was stirred at room temperature for 12 hours and then carefully poured into 200 mL of 5% NaHCO3. The crude product was extracted with dichloromethane (3 x 50 ml), and the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. 11.4 g (99%) of a white solid was obtained. 1 H NMR (CDCl3, 400MHz): δ7.17 (d, J = 2.0Hz, 1H), 6.99 (d, J = 2.0Hz, 1H), 5.65 (s, 1H), 2.28 (s, 3H), 1.67 (s.6H), 1.10-1.21 (m, 6H), 0.91 (s, 9H). 13 C NMR (CDCl3, 100MHz): δ148.1, 136.5, 130.3, 129.4, 127.3, 112.1, 50.3, 45.8, 39.9, 32.1, 30.5, 20.6.

[0187] 1-(3-Bromo-2-(methoxymethoxy)-5-methylphenyl)-3,5,7-trimethyladamantane To a solution of 11.4 g (31.4 mmol) of 2-bromo-4-methyl-6-(3,5,7-trimethyladamantan-1-yl)phenol in 100 ml of dry THF at room temperature was added 1.06 g (34.9 mmol, 60 wt. % in mineral oil) of sodium hydride. Thereafter, 2.65 ml (34.9 mmol) of methoxymethyl chloride were added in one portion. The reaction mixture was heated at 60° C. for 24 hours and then poured into 130 ml of cold water. The crude product was extracted with 3×20 ml of dichloromethane. The combined organic extracts were dried over Na2SO4 and then evaporated to dryness. This yielded 11.9 g (91%) of a pale yellow solid. 1 H NMR (CDCl3, 400MHz): δ7.25 (d, J = 2.0Hz, 1H), 7.06 (d, J = 2.0Hz, 1H), 5.23 (s, 2H),3.71(s,3H),2.29(s,3H),1.68(s,6H),1.10-1.21(m,6H),0.92(s,9H). 13 C NMR (CDCl3, 100MHz): δ151.3,144.0,134.4,131.9,127.4,117.6,99.9,57.8,50.2,46.8,40.3,32.2,30.6,20.7.

[0188] 2-(2-(Methoxymethoxy)-5-methyl-3-(3,5,7-trimethyladamantan-1-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane To a solution of 12.4 g (30.5 mmol) of 1-(3-bromo-5-methyl-2-(methoxymethoxy)phenyl)-3,5,7-trimethyladamantane in 200 ml of dry THF was added dropwise 14.6 ml (30.5 mmol) of 2.5 M 2-(methoxymethoxy)phenyl-3,5,7-trimethyladamantane in hexane at -80°C over 20 minutes. n BuLi. The reaction mixture was stirred at this temperature for 1 hour and then 9.33 ml (45.7 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 and then poured into 130 ml of water. The crude product was extracted with dichloromethane (3×40 ml), the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. 12.9 g (93%) of a white solid were obtained. 1 H NMR (CDCl3, 400MHz): δ7.39 (d, J = 1.9 Hz, 1H), 7.22 (d, J = 1.9 Hz, 1H), 5.16 (s, 2H), 3. 61(s,3H),2.31(s,3H),1.72(s,6H),1.38(s,12H),1.09-1.18(m,6H),0.90(s,9H). 13 C NMR (CDCl3, 100MHz): δ159.8,140.4,134.7,131.6,131.2,101.2,83.6,57.9,50.4,46.7,39.5,32.2,30.6,24.74,20.8.

[0189] 1-(2'-bromo-2-(methoxymethoxy)-5-methyl-[1,1'-biphenyl]-3-yl)-3,5,7-trimethyladamantane Then, 4.50 g (9.90 mmol) of 2-(5-methyl-2-(methoxymethoxy)-3-(3,5,7-trimethyladamantan-1-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added to 20 ml of 1,4-dioxaborolane. 2.80 g (9.90 mmol) of 2-bromoiodobenzene, 3.42 g (24.8 mmol) of potassium carbonate and 10 ml of water were added to the solution in alkane. The obtained mixture was purged with argon for 10 minutes, and then 286 mg (0.25 mmol) of Pd (PPh 3 ) 4 was added. This mixture was stirred at 105° C. for 12 hours, then cooled to room temperature and diluted with 100 ml of water. The crude product was extracted with dichloromethane (3×50 ml), and the combined organic extracts were dried over Na 2 SO 4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, volume). 3.90 g (82%) of white solid was produced. 1 H NMR (CDCl3, 400MHz): δ7.73(dd,J=8.0,0.9Hz,1H),7.38-7.46(m,2H),7.24-7.28(m,1H),7.23(d,J=1.6Hz,1H),6.97(d,J =1.6Hz,1H),4.56-4.58(m,1H),4.47-4.48(m,1H),3.31(s,3H),2.41(s,3H),1.80(s,6H),1.17-1.29(m,6H),0.98(s,9H). 13 C NMR (CDCl3, 100MHz): δ151.9,141.8,141.1,134.5,132.9,132.2,132.0,130. 0,128.6,127.8,127.1,124.0,99.1,57.1,50.3,46.8,39.8,32.2,30.7,21.1.

[0190] 2-(2'-(methoxymethoxy)-5'-methyl-3'-(3,5,7-trimethyladamantan-1-yl)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane To a solution of 3.80 g (7.86 mmol) of 1-(2'-bromo-5-methyl-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)-3,5,7-trimethyladamantane in 40 ml of dry THF at -80°C was added dropwise 4.10 mL (10.2 mmol) of 2.5 M arginine in hexane over 20 minutes. nBuLi. The reaction mixture was stirred at this temperature for 1 hour, then 2.57 ml (12.6 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 100 ml of water. The crude product was extracted with dichloromethane (3×100 ml), and 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 μm, eluent: hexane-diethyl ether=10:1, volume). 3.71 g (90%) of colorless glassy solid was produced. 1 H NMR (CDCl3, 400MHz): δ7.78 (dd, J=7.4, 1.0Hz, 1H), 7.32-7.45 (m, 3H), 7.11 (d, J=1.9Hz, 1H), 6.89 (d, J=1 .9Hz,1H),4.41-4.48(m,2H),3.32(s,3H),2.33(s,3H),1.79(br.s,6H),1.13-1.25(m,18H),0.94(s,9H). 13 C NMR (CDCl3, 100MHz): δ151.9,145.6,141.1,136.6,134.4,131.5,130.5,130.3,129.9 ,126.7,126.1,98.9,83.4,57.2,50.4,47.0,39.7,32.2,30.7,25.2,24.8,24.1,21.0.

[0191] 2',2"'-(4-(Pyrrolidin-1-yl)pyridine-2,6-diyl)bis(5-methyl-3-(3,5,7-trimethyladamantan-1-yl)-[1,1'-biphenyl]-2-phenol) Then, 4.24 g (8.00 mmol) of 2-(3'-(3,5,7-trimethyladamantan-1-yl)-2'-(methoxymethoxy)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added to 20 ml of 1,4-dioxaborolane. 1.22 g (4.00 mmol) of 2,6-dibromo-4-(pyrrolidin-1-yl)pyridine, 6.64 g (20.0 mmol) of cesium carbonate and 10 ml of water were added to the solution in oxane. The obtained mixture was purged with argon for 10 minutes, and then 460 mg (0.40 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 mixture thus obtained was extracted with dichloromethane (3×50 ml), and the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. Subsequently, 20 ml of THF, 20 ml of methanol and 4 ml of 12M HCl were added to the resulting oil. The reaction mixture was stirred at 60°C overnight and then poured into 200 ml of water. The crude product was extracted with dichloromethane (3×70 mL), and the combined organic extracts were washed with 5% NaHCO3, dried over Na2SO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: dichloromethane-ethyl acetate = 3:1, volume). 1.86 g (54%) of a mixture of two isomers was obtained as a white foam. 1 H NMR (CDCl3, 400 MHz): δ 8.00 (s, 2H in A), 7.97 (s, 2H in B), 7.64 (d, J = 7.2 Hz, 2H in A), 7.59-7.61 (m, 2H in B), 7.41-7.51 (m, 4H in A, 4H in B), 7.33 (d, J = 7.5 Hz, 1H in A), 7.27-7.29 (m, 1H in B), 6.93 (s, 2H in A), 6.92 (s, 2H in B), 6.88 (s, 2H in A), 6.46 (s, 2H in B), 6.07 (s, 2H in B ),6.01(s, 2H in A),2.96-3.08(m, 4H in B),2.83(br.s, 4H in A),2.29(s, 6H in A),2.10(s, 6H in B),1.85-1.94(m, 4H in A, 4H in B),1.56(br.s, 4H in A, 4H in B),1.24-1.40(m, 8H in A, 8H in B),1.02-1.09(m, 12H in B),0.88-0.96(m, 12H in A),0.79(s, 18H in B),0.68(s, 18H in A). 13C NMR (CDCl3, 100 MHz, minor isomer resonances marked with asterisks): δ 157.5*, 157.3, 151.9*, 151.8, 150.3*, 149.8, 140.7*, 139.6, 137.2, 137.0*, 136.8, 132.2, 131.6, 131.2*, 130.6, 130.3, 130.2*, 129.2, 129.0, 1 28.9*,128.6*,128.5,128.2*,127.68*,127.64,126.6,126.5*,106.0*,105.7,50.5*,50.2,46.9*,46.5,46.3*,46.0,39.4*,39.1,32.0*,31.9,30.7*,30.5,25.3,25.0*,21.0,20.7*.

[0192] 2-(3,5-Dimethyladamantan-1-yl)-4-methylphenol To a solution of 8.10 g (75.0 mmol) of 4-methylphenol and 13.5 g (75.0 mmol) of 3,5-dimethyladamantan-1-ol in 150 ml of dichloromethane was added dropwise a solution of 4.90 ml (75.0 mmol) of methanesulfonic acid and 5 ml of acetic acid in 100 ml of dichloromethane over 1 hour at room temperature. The resulting mixture was stirred at room temperature for 12 hours and then carefully poured into 300 ml of 5% NaHCO3. The resulting mixture was extracted with dichloromethane (3 x 50 ml), the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residue was purified using a Kugelrohr apparatus (1 mbar, 70°C) to give 14.2 g (70%) of the title product as a light yellow oil. 1 H NMR (CDCl3, 400MHz): δ7.02 (s, 1H), 6.86 (dd, J = 8.0, 1.5Hz, 1H), 6.54 (d, J = 8.0Hz, 1H), 4.61 (s, 1H), 2.27 (s, 3H),2.14-2.19(m,1H),1.95(br.s,2H),1.65-1.80(m,4H),1.34-1.48(m,4H),1.21(br.s,2H),0.88(s,6H). 13 C NMR (CDCl3, 100MHz): δ152.0,135.5,129.7,127.7,127.0,116.6,51.1,46.8,43.2,39.0,38.3,31.4,30.9,30.0,20.8.

[0193] 2-Bromo-6-(3,5-dimethyladamantan-1-yl)-4-methylphenol To a solution of 14.2 g (52.5 mmol) of 2-(3,5-dimethyladamantan-1-yl)-4-methylphenol in 200 ml of dichloromethane at room temperature, a solution of 2.70 ml (52.5 mmol) of bromine in 100 ml of dichloromethane was added dropwise over 1 hour. The resulting mixture was stirred at room temperature for 12 hours and then carefully poured into 200 mL of 5% NaHCO3. The resulting mixture was extracted with dichloromethane (3×50 ml), and the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. 17.0 g (92%) of a light yellow solid was produced. 1 H NMR (CDCl3, 400MHz): δ7.16 (d, J = 2.0Hz, 1H), 6.97 (d, J = 1.8Hz, 1H), 5.64 (s, 1H), 2.27 (s, 3H), 2.14 -2.20(m,1H),1.94(br.s,2H),1.67-1.79(m,4H),1.35-1.47(m,4H),1.21(br.s,2H),0.88(s,6H). 13 C NMR (CDCl3, 100MHz): δ148.2,136.8,130.3,129.4,127.3,112.1,51.0,46.4,43.1,39.1,38.7,31.4,30.9,30.0,20.6.

[0194] 1-(3-Bromo-5-methyl-2-(methoxymethoxy)phenyl)-3,5-dimethyladamantane To a solution of 17.0 g (48.7 mmol) of 2-bromo-6-(3,5-dimethyladamantan-1-yl)-4-methylphenol in 200 ml of dry THF was added portionwise 1.95 g (50.0 mmol, 60 wt. % in mineral oil) of sodium hydride at room temperature. Thereafter, 4.00 ml (53.0 mmol) of methoxymethyl chloride was added dropwise for 1 hour. The reaction mixture was heated at 60° C. for 24 hours and then poured into 300 ml of cold water. The crude product was extracted with 3×200 ml of dichloromethane. The combined organic extracts were dried over Na2SO4 and then evaporated to dryness. 17.2 g (90%) of a white solid were obtained. 1H NMR (CDCl3, 400MHz): δ7.22(d,J=1.5Hz,1H),7.04(d,J=1.5Hz,1H),5.21(s,2H),3.69(s,3H),2.26(s,3 H),2.11-2.19(m,1H),1.92(br.s,2H),1.65-1.80(m,4H),1.34-1.43(m,4H),1.20(s,2H),0.87(s.6H). 13 C NMR (CDCl3, 100MHz): δ151.21,144.4,134.4,131.9,127.5,117.6,99.8,57.9,50.9,47.5,43.0,39.8,39.5,31.5,31.0,30.0,20.7.

[0195] 2-(3-(3,5-dimethyladamantan-1-yl)-5-methyl-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane To a solution of 12.8 g (32.4 mmol) of 1-(3-bromo-5-methyl-2-(methoxymethoxy)phenyl)-3,5-dimethyladamantane in 200 ml of dry THF at -80°C, 14.3 ml (35.6 mmol) of 2.5 M 2-(methoxymethoxy)phenyl)-3,5-dimethyladamantane was added dropwise over 20 minutes. n BuLi. The reaction mixture was stirred at this temperature for 1 hour, then 10.0 ml (48.7 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. The crude product was extracted with dichloromethane (3×100 ml), the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residue was recrystallized from isopropanol. 11.1 g (78%) of a white solid was produced. 1 H NMR (CDCl3, 400MHz): δ7.37(d,J=1.8Hz,1H),7.20(d,J=2.0Hz,1H),5.14(s,2H),3.60(s,3H),2.29(s,3H),2.1 1-2.18(m,1H),1.97(br.s,2H),1.69-1.84(m,4H),1.34-1.47(m,4H),1.36(s,12H),1.20(s,2H),0.87(s,6H). 13C NMR (CDCl3, 100MHz): δ159.8,140.7,134.7,131.7,131.2,101.1,83.7,57.9,51.1,47.4,43.2,39.7,38.7,31.5,31.0,30.1,24.8,20.8.

[0196] 1-(2'-bromo-2-(methoxymethoxy)-5-methyl-[1,1'-biphenyl]-3-yl)-3,5-dimethyladamantane Then, 3.02 g (6.86 mmol) of 2-(5-methyl-2-(methoxymethoxy)-3-(3,5-dimethyladamantan-1-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added to 9 ml of 1,4-dioxaborolane. 1.94g (6.86mmol) 2-bromoiodobenzene, 5.59g (17.1mmol) cesium carbonate and 4ml water were added to the solution in alkane. The obtained mixture was purged with argon for 10 minutes, and then 396mg (0.343mmol) of Pd (PPh3)4 was added. This mixture was stirred at 105°C for 12 hours, then cooled to room temperature and diluted with 100ml water. The crude product was extracted with dichloromethane (3×50ml), and the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63μm, eluent: hexane-dichloromethane=10:1, volume). 1.64g (51%) yellow oil was produced. 1 H NMR (CDCl3, 400MHz): δ7.72 (d, J=7.9Hz, 1H), 7.42 (dt, J=7.6, 1.8Hz, 1H), 7.39 (t, J=7.5Hz ,1H),7.20-7.26(m,1H),7.21(d,J=1.9Hz,1H),6.95(d,J=1.9Hz,1H),4.55(d,J=4.7Hz,1H AB),4.48(d,J=4.7Hz,1HAB),3.28(s,3H),2.39(s,3H),2.21-2.26(m,1H),2.01- 2.08(m,2H),1.77-1.95(m,4H),1.40-1.54(m,4H),1.28(br.s,2H),0.95(s,6H). 13C NMR (CDCl3, 100MHz): δ151.8,142.1,141.2,134.5,132.8,132.2,132.1,130.0,128.6,127.8 ,127.1,124.0,99.0,57.0,51.0,47.5,47.45,43.2,43.1,39.7,38.9,31.5,31.0,30.1,21.0.

[0197] 2-(3'-(3,5-dimethyladamantan-1-yl)-2'-(methoxymethoxy)-5'-methyl-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane To a solution of 1.64 g (3.56 mmol) of 1-(2'-bromo-2-(methoxymethoxy)-5-methyl-[1,1'-biphenyl]-3-yl)-3,5-dimethyladamantane in 50 ml of dry THF at -80°C was added dropwise 1.71 ml (4.27 mmol) of 2.5 M arginine in hexane over 20 minutes. n BuLi. The reaction mixture was stirred at this temperature for 1 hour, then 1.09 ml (5.34 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 100 ml of water. The crude product was extracted with dichloromethane (3×100 ml), the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. 1.74 g (99%) of a colorless glassy solid were obtained. 1 H NMR (CDCl3, 400MHz): δ7.76 (dd, J=7.4, 1.0Hz, 1H), 7.41-7.45 (m, 1H), 7.35-7.38 (m, 1H), 7.32 (dt, J=7.4, 1.3Hz, 1H), 7.08 (d, J=2.0Hz, 1H), 6.85 (d, J=2.0Hz,1H),4.38-4.47(m,2H),3.29(s,3H),2.31(s,3H),2.18-2.22(m,1 H),1.73-2.05(m,6H),1.35-1.52(m,4H),1.17-1.22(m,12H),0.91(s,6H). 13C NMR (CDCl3, 100MHz): δ151.7,145.6,141.4,136.7,134.4,131.6,130.5,130.3,129.9,126.7,1 26.1,98.9,83.4,57.3,51.0,47.8,47.6,43.2,39.9,38.9,31.5,31.0,30.2,25.1,24.1,21.0.

[0198] 2',2"'-(4-(Pyrrolidin-1-yl)pyridine-2,6-diyl)bis(3-(3,5-dimethyladamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenol) Then, 0.87 g (1.68 mmol) of 2-(3'-(3,5-dimethyladamantan-1-yl)-2'-(methoxymethoxy)-5'-methyl-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added to 4 ml of 1,4-dioxaborolane. 206 mg (0.674 mmol) of 2,6-dibromo-4-(pyrrolidin-1-yl)pyridine, 1.37 g (4.21 mmol) of cesium carbonate and 2 ml of water were added to the solution in oxane. The obtained mixture was purged with argon for 1 minute and then 100 mg (0.0842 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 30 ml of water. The mixture thus obtained was extracted with dichloromethane (3×50 ml), the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. 20 ml of THF, 20 ml of methanol and 2 ml of 12N HCl were subsequently added to the resulting oil. The reaction mixture was stirred at 60°C overnight and then poured into 200 ml of water. The crude product was extracted with dichloromethane (3×70 mL), the combined organic extracts were washed with 5% NaHCO3, dried over Na2SO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate = 10:1, volume). This gave 0.49 g (87%) of a mixture of two isomers as a white foam. 1HNMR (CDCl3, 400MHz): δ8.53 (br.s, 2H in B), 8.28 (br.s, 2H in A), 7.56-7.66 (m, 2H in A, 2H in B), 7.28-7.46 (m, 9H in A and B), 6.85-6.88 (m, 4H in A and B), 6.30 (s, 2H in B), 6.07 (s, 2H in B), 5.98 (s, 2H in A), 2.98-3.12 (m, 4H in B), 2.80-2.90 (m, A s, 4H in A), 2.26(s, 6H in A), 2.02(s, 6H in B), 1.84-1.94(m, 6H in A and B), 1.50-1.80(m, 6H in A and B), 1.35-1.47(m, 4H in A and B), 1.10-1.30(m, 10H in A and B), 0.91-1.05(m, 4H in A and B), 0.81(s, 6H in B), 0.79(s, 6H in B), 0.71(s, 6H in A), 0.70(s, 6H in A). 13 C NMR(CDCl3,100MHz)δ150.1,139.2,137.7,137.2,132.2,131.5*,131.4*,130.8*,130.2 ,130.1*,129.6*,129.2,129.1,128.8*,128.4*,128.35,127.6,127.5*,126.5,126.3*,1 25.8*,105.9*,105.8,51.2*,51.0,47.6*,47.0,46.6,46.2,43.3*,43.0,42.8*,42.7,38.5*,38.4,38.2,38.1,31.4*,31.2,31.1,30.9*,30.2*,30.1*,25.3,25.1*,21.0,20.7*. Preparation of transition metal complexes

[0199] Complex 3 To a mixture of ZrCl4(Et2O)2 (50 mg, 0.131 mmol) and 2',2"'-(4-methylpyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (100 mg, 0.123 mmol) in toluene (~mL) was added MeMgBr (3.0 M, 0.18 mL, 0.54 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 on a glass fiber plug. The filtrate was concentrated under vacuum to a brown foam. The crude product was recrystallized from pentane at -40°C, allowing slow evaporation. Yield 29.0 mg (product was isolated using 1 equivalent of pentane). 1 H NMR (C6D6, 400MHz): δ7.54 (d, J = 2.4Hz, 2H), 7.25-6.96 (m, 10H), 6.21 (s, 2H), 2.73-2.38 (m ,12H),2.19(br,6H),2.06-1.77(m,12H),1.32(d,J=1.3Hz,18H),1.19(s,3H),0.13(s,6H).

[0200] Complex 4 To a pre-cooled stirred suspension of zirconium chloride (0.142 g, 0.609 mmol, 1 eq) in toluene (2 mL) was added methylmagnesium bromide (0.82 mL, 3.0 M in diethyl ether, 2.5 mmol, 4.0 eq). Then, a pre-cooled solution of 2',2"'-(4-ethylpyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (0.502 g, 0.609 mmol) in toluene (3 mL) was added dropwise. The reaction was stirred at room temperature for 3 hours. The reaction was concentrated under a nitrogen stream and then under high vacuum. The residue was stirred in hexanes (20 mL) and heated to reflux. The mixture was filtered through Celite while hot. The filtrate was further extracted with refluxing hexanes (2×20 mL). The combined hexane filtrates were concentrated under a nitrogen stream and then under high vacuum to give the product as a brown-grey solid containing hexanes (0.18 equiv.) and toluene (0.96 equiv.) (0.424 g, 66% yield). 1 H NMR (C6D6, 400MHz): δ7.54 (d, 2H, J = 2.6Hz), 7.24-7.20 (m,2H),7.14-7.00(m,8H),6.39(s,2H),2.65-2.54(m,6H),2.49-2.40(m,6H),2.24-2.15(m,6H),2.06- 1.96(m,6H),1.89-1.80(m,6H),1.68(q,2H,J=7.6Hz),1.33(s,18H),0.48(t,3H,J=7.6Hz),0.14(s,6H).

[0201] Complex 5 To a suspension of 98 mg (0.307 mmol) of hafnium tetrachloride in 20 mL of dry toluene at 0°C was added 476 μL (1.39 mmol) of 2.9 M MeMgBr in diethyl ether in one portion via syringe. To the resulting suspension was immediately added 237 mg (0.307 mmol) of 2',2"'-(4-(ethylthio)pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenol in one portion. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The solid obtained was extracted with 2×20 mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. The filtrate was then evaporated to dryness. 217 mg (72%) of a white solid was produced. 55 H 61 Anal. Calc. for HfNSO2: C, 67.50; H, 6.28; N, 1.43. Found: C 67.88; H, 6.36; N 1.27. 1 H NMR(C6D6,400MHz): δ7.09-7.22(m,10H),6.80(d,J=1.7Hz,2H),6.48(s,2H),2.45-2.52(m,6H),2.31-2.38(m,6H),2.2 3(s,6H),2.18(br.s,6H),1.96-2.02(m,6H),1.80-1.87(m,6H),1.69-1.83(m,2H),0.54(t,J=7.4Hz,3H),-0.14(s,6H). 13 C NMR(C6D6,100MHz)δ160.0,157.2,155.7,143.7,139.2,133.7,133.3,132.8,13 1.6,131.2,129.3,127.1,120.9,51.0,41.9,38.1,37.9,30.0,24.7,21.4,12.6.

[0202] Complex 6 To a mixture of ZrCl4 (115 mg, 0.493 mmol) and 2',2"'-(4-butylpyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (400 mg, 0.469 mmol) in toluene (~5 mL) was added MeMgBr (3.0 M, 0.7 mL, 2.1 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 2 hours and then evaporated to dryness. The resulting solid was extracted with isohexane and the combined extracts were filtered through Celite on a glass fiber plug. The filtrate was concentrated under vacuum to a brown residue. The product was further purified by slow evaporation of the precipitate from a pentane solution at ambient temperature and then at -40°C. The brown supernatant was decanted from the precipitate and washed with cold pentane until the washings were almost colorless. A white solid containing 0.75 equivalents of pentane was produced (64.1 mg). 1 H NMR(400MHz,C6D6)δ7.53(s,2H),7.26-7.20(m,2H),7.15-6.98(m,8H),6.37(s,2H),2.70-2.30(m,12H),2.19(s,6H) ,2.06-1.74(m,12H),1.75(dt,J=11.2,7.4Hz,2H),1.33(s,18H),1.24(m,2H),0.73(m,2H),0.64(t,3H),0.12(s,6H).

[0203] Complex 7 To a mixture of ZrCl4 (60 mg, 0.257 mmol) and 2',2"'-(4-((tert-butyldimethylsilyl)methyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (200 mg, 0.216 mmol) in toluene (~3 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.35 mL, 1.05 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 16 hours and then evaporated to dryness. The resulting solid was extracted with isohexane (total ~ 30mL) and the extract was filtered through Celite on a glass fiber plug. The combined filtrate was concentrated under vacuum to a brown foam (183.5mg). The product was further purified by precipitation by slow evaporation from a pentane solution at -40°C. The brown supernatant was decanted from the precipitate and dried under vacuum. Produced (95.6mg) of a brown solid. 1H NMR (400MHz, C6D6) δ7.55(d,J=2.5Hz,2H),7.13(d,J=18.0Hz,10H),6.25(s,2H),2.69-2.32(m,12H),2.20(s,6H),2 .08-1.71(m,12H),1.37(s,18H),0.85(dd,J=8.6,6.3Hz,2H),0.67(s,9H),0.12(s,6H),-0.46(s,3H),-0.62(s,3H).

[0204] Complex 8 To a mixture of ZrCl4(Et2O)2 (80.9 mg, 0.212 mmol) and 2',2"'-(4-((triethylsilyl)methyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (187 mg, 0.202 mmol) in toluene (~3 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.3 mL, 0.9 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 1 hour and then evaporated to dryness. The resulting solid was extracted with pentane (~10 mL total) and the combined extracts were filtered through Celite on a glass fiber plug. The filtrate was concentrated under vacuum to a brown foam. The product was further purified by recrystallization from pentane at -40°C. Yield: 31.9 mg (product isolated with 0.5 equivalents of pentane). 1 H NMR (400MHz, C6D6) δ7.56 (d, J = 2.5Hz, 2H), 7.33-6.98 (m, 10H), 6.38 (s, 2H), 2.73-2.31 (m, 12H), 2.21 (s, 6H), 2.07-1 .74(m,12H),1.52(s,2H),1.38(s,18H),1.31-1.09(m,3H),0.88(t,J=7.0Hz,3H),0.62(t,J=7.9Hz,9H),0.13(s,6H).

[0205] Complex 9 To a mixture of ZrCl4(Et2O)2 (60 mg, 0.157 mmol) and 2',2"'-(4-((trihexylsilyl)methyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (155 mg, 0.142 mmol) in toluene (~4 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.22 mL, 0.66 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 14 h and then evaporated to dryness. The resulting solid was extracted with pentane (~10 mL total) and the combined extracts were filtered through Celite on a glass fiber plug. The filtrate was concentrated under vacuum to a brown foam. 1 H NMR(400MHz,C6D6)δ7.57(d,J=2.6Hz,2H),7.31-6.71(m,10H),6.50(s,2H),2.71-2.37(m,12H),2.18(s,6H),2.06 -1.73(m,12H),1.59-1.04(m,44H),0.93(t,J=7.0Hz,9H),0.61(s,3H),0.27(dd,J=10.2,6.4Hz,6H),0.14(s,3H).

[0206] Complex 10 To a suspension of 184 mg (0.576 mmol) of hafnium tetrachloride in 60 mL of dry toluene at 0 °C was added 834 μL (2.42 mmol) of 2.9 M MeMgBr in diethyl ether in one portion via syringe. To the resulting suspension were added 450 mg (0.576 mmol) of 2',2"'-(4-(pyrrolidin-1-yl)pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenol at once. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The solid obtained was extracted with 2×20 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 and the precipitate obtained was filtered off (G4), washed twice with 5 mL of n-hexane and then dried in vacuo. This yielded 512 mg (90%) of a white-beige solid. C 57 H 64 Calcd. for HfN2O2: C, 69.32; H, 6.53; N, 2.84. Found: C 69.67; H, 6.82; N 2.55. 1H NMR (C6D6, 400MHz): δ7.39-7.41(m,2H),7.18-7.30(m,8H),6.92(d,J=1.7Hz,2H),5.64(s,2H),2.53-2.60(m,6H),2.39-2.46( m,6H),2.27(s,6H),2.21(br.s,6H),2.00-2.06(m,6H),1.93-1.98(m,4H),1.82-1.89(m,6H),0.87-0.91(m,4H),-0.08(s,6H). 13 C NMR(C6D6,100MHz)δ159.6,157.0,152.9,143.2,138.8,133.4,133.3,133.28,131.4 ,130.9,129.5,127.9,126.5,107.3,49.1,48.0,41.4,37.7,37.6,29.8,25.7,21.0.

[0207] Complex 11 To a mixture of ZrCl4(Et2O)2 (54 mg, 0.142 mmol) and 2',2"'-(4-(tert-butyloxy)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) (116 mg, 0.134 mmol) in toluene (~3 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.2 mL, 0.6 mmol) dropwise. 1). The reaction mixture was stirred at ambient temperature for 70 minutes and then evaporated to dryness. The solid was stirred with n-pentane (~20 mL) and the resulting mixture was filtered through a plastic fritted funnel. The filtrate was rinsed with additional pentane (2×5 mL). The combined filtrates were concentrated under vacuum to a solid. The resulting product was redissolved in n-pentane (~20 mL total) and filtered through a glass fiber plug. The resulting solution was concentrated under vacuum to a brown solid (69.3 mg, 52%).

[0208] Complex 12 To a mixture of ZrCl4(Et2O)2 (53 mg, 0.139 mmol) and 2',2"'-(4-(3-butenyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (114 mg, 0.134 mmol) in toluene (~5 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.2 mL, 0.6 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 1 hour and then evaporated to dryness. The resulting solid was extracted with n-hexane (~10 mL x 2) and the combined extracts were filtered through a medium glass fritted funnel. The filtrate was concentrated under vacuum to a brown solid. The resulting solid was dissolved in n-hexane (~10 mL total) and filtered through a glass fiber plug. The resulting filtrate was concentrated under vacuum to a brown solid (110.5 mg, 85%). 1 H NMR (400MHz, C6D6) δ7.53(d,J=2.7Hz,2H),7.25-7.00(m,10H),6.28(s,2H),5.18(ddt,J=17.1,10.2,6.7Hz,1H),4.74(d,J=9.5Hz,1H),4.4 6(d,J=17.1,1H),2.65-2.31(m,12H),2.19(s,6H),2.08-1.79(m,12H) ,1.76-1.51(m,2H),1.33(s,18H),0.88(t,J=6.9Hz,2H),0.12(s,6H).

[0209] Complex 13 To a mixture of ZrCl4(Et2O)2 (38 mg, 0.1 mmol) and 2',2"'-(4-propylpyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (81 mg, 0.097 mmol) in toluene (~5 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.14 mL, 0.42 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 70 minutes and then evaporated to dryness. The resulting solid was extracted with n-hexane (~10 mL x 2) and the combined extracts were filtered through a medium glass sintered funnel. The filtrate was concentrated under vacuum to a brown solid. The resulting solid was dissolved in n-hexane (~10 mL total) and filtered through a glass fiber plug. The resulting filtrate was concentrated under vacuum to a brown solid (68.2 mg, 74%).

[0210] Complex 14 To a mixture of ZrCl4(Et2O)2 (55 mg, 0.144 mmol) and 2',2"'-(4-(tert-butyldimethylsilyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (122 mg, 0.134 mmol) in toluene (~5 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.2 mL, 0.6 mmol) dropwise. The reaction mixture was stirred at 40°C. The mixture was stirred at ambient temperature for 1 hour and then evaporated to dryness. The solid was extracted with methylcyclohexane (total 20 mL) and the combined extracts were filtered through a plastic porous funnel. The filtrate was rinsed with additional methylcyclohexane (2×5 mL). The combined filtrate was concentrated under vacuum to 5 mL and then filtered through a glass fiber plug. The filtrate was concentrated under vacuum to a brown solid which was subsequently recrystallized from hot isohexane to give colorless crystals which were dried under vacuum. 87.5 mg of a white powder containing 1 equivalent of isohexane was produced.

[0211] Complex 15 To a mixture of ZrCl4(Et2O)2 (57 mg, 0.149 mmol) and 2',2"'-(4-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (135 mg, 0.135 mmol) in toluene (~5 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.2 mL, 0.6 mmol) dropwise. The reaction mixture was stirred at 40°C. The product was stirred at ambient temperature for 90 minutes and then evaporated to dryness. The obtained solid was extracted with pentane (total ~ 20mL) and the combined extracts were filtered through a plastic porous funnel. The filtrate was rinsed with additional pentane (2×10mL). The combined filtrate was concentrated under vacuum to a solid, which was then redissolved in pentane (total 10mL) and filtered through Celite on a glass fiber plug. The filtrate was concentrated under vacuum to a tan solid (132.4mg). The solid was further purified by precipitation from pentane at -40°C to obtain a white solid.

[0212] Complex 16: Synthesis of [2',2"'-(4-(tert-butyl)-thiopyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenolate)] dimethylzirconium To a pre-cooled stirred suspension of zirconium tetrachloride (57 mg, 0.25 mmol, 1 eq) in toluene (3 mL) was added methylmagnesium bromide (0.33 mL, 3.0 M in diethyl ether, 0.99 mmol, 4.1 eq). Then, a pre-cooled solution of 2',2"'-(4-(tert-butyl)-thiopyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (214 mg, 0.24 mmol) in toluene (5 mL) was added. The reaction was stirred at room temperature for 1 hour. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (10 mL, then 5 mL) and filtered on Celite. The combined pentane extracts were cooled to -35°C. The resulting precipitate was collected and concentrated under high vacuum to give the product as a white solid containing toluene (0.39 equiv.) (104 mg, 41% yield). 1 H NMR (400MHz, C6D6): δ7.55 (d, 2H, J = 2.6Hz), 7.21 (d, 2H, J = 7.3Hz), 7.12-6.99 (m, 8H), 6.95 (s, 2H), 2.59-2.51 (m, 6H) ,2.45-2.37(m,6H),2.22-2.16(m,6H),2.03-1.94(m,6H),1.89-1.80(m,6H),1.33(s,18H),0.86(s,9H),0.11(s,6H).

[0213] Complex 17: Synthesis of [2',2"'-(4-(butylthio)-pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)]dimethylzirconium To a pre-cooled stirred suspension of zirconium tetrachloride (65 mg, 0.28 mmol, 1 eq) in toluene (2 mL) was added methylmagnesium bromide (0.38 mL, 3.0 M in diethyl ether, 1.1 mmol, 4.1 eq). Then, a solution of 2',2"'-(4-(butylthio)-pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (246 mg, 0.278 mmol) in toluene (2 mL) was added. The reaction was stirred at room temperature for 24 hours. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2×10 mL) and filtered on Celite. The combined pentane extracts were cooled to -35°C. The resulting supernatant was collected and concentrated under a stream of nitrogen and then under high vacuum. The residue was dissolved in minimal pentane and cooled to -35°C. The resulting precipitate was collected and concentrated under high vacuum to give a solid product (57 mg, 20% yield) containing toluene (0.41 equiv). 1 H NMR (400MHz, C6D6): δ7.56 (dd, 2H, J = 10.3, 2.6Hz), 7.24-7.18 (m, 2H), 7.14-6.99 (m, 8H), 6.53 (s, 1H), 6.23 (s, 1H), 2.65-2.55 (m, 6H), 2.50 -2.41(m,6H),2.24-2.16(m,6H),2.09-1.91(m,8H),1.89-1.80(m,6H) ,1.36-1.16(m,22H),0.61(t,3H,J=7.2Hz),0.14(s,3H),0.13(s,3H).

[0214] Complex 18: Synthesis of [2',2"'-(4-(dodecylthio)-pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)]dimethylzirconium To a precooled stirred suspension of zirconium tetrachloride (21 mg, 90 mol, 1 eq) in toluene (1 mL) was added methylmagnesium bromide (0.12 mL, 3.0 M in diethyl ether, 0.36 mmol, 4 eq). Then, a pre-cooled solution of 2',2"'-(4-(dodecylthio)-pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (90 mg, 90 μmol) in toluene (2 mL) was added. The reaction was stirred at room temperature for 15 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2×3 mL) and filtered on Celite. The combined pentane extracts were cooled to -35°C. The resulting turbid mixture was filtered. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give the product as a glassy solid, which formed a white solid upon abrasion (60 mg, 59% yield). 1 H NMR (400MHz, C6D6): δ7.58(d,2H,J=2.6Hz),7.22-7.18(m,2H),7.13-7.01(m,8H),6.56(s,2H),2.65-2.56(m,6H),2.51-2.43(m,6H) 2.23-2.16(m,6H),2.15-2.08(m,2H),2.06-1.97(m,6H),1.90-1.81(m,6H),1.39-1.07(m,38H),0.92(t,3H,J=7.0Hz),0.13(s,6H).

[0215] Complex 19 To a mixture of ZrCl4(Et2O)2 (55.2 mg, 0.145 mmol) and 2',2"'-(4-(4-tert-butylphenyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (123 mg, 0.132 mmol) in toluene (~3 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.2 mL, 0.6 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 70 minutes and then evaporated to dryness. The resulting solid was extracted with methylcyclohexane (~10 mL total) and the combined extracts were filtered through Celite. The filtrate was then concentrated under vacuum to a solid.

[0216] Complex 20: Synthesis of [2',2"'-(4-(diisopropylamino)methylpyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenolate)]zirconium dimethyl To a pre-cooled stirred suspension of zirconium tetrachloride (27 mg, 0.12 mmol, 1 eq) in toluene (2 mL) was added methylmagnesium bromide (0.16 mL, 3.0 M in diethyl ether, 0.48 mmol, 4.2 eq). Then, a pre-cooled solution of 2',2"'-(4-((diisopropylamino)methyl)-pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (104 mg, 0.114 mmol) in toluene (2 mL) was added. The reaction was stirred at room temperature for 18.5 hours. The reaction was concentrated at 50°C under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (15 mL) and then toluene (5 mL) and filtered on Celite. The combined extracts were concentrated under a stream of nitrogen and then under high vacuum. The residue was further extracted with hot hexanes and filtered on Celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give the product as a tan solid containing hexanes (2.63 equiv.) and toluene (0.28 equiv.) (71.2 mg, 48% yield). 1 H NMR (400MHz, C6D6): δ7.53(d,2H,J=2.6Hz),7.26-7.23(m,2H),7.14-7.09(m,8H),6.93(s,2H),2.97-2.80(m,2H),2.60-2.50(m,8H),2.47- 2.38(m,6H),2.24-2.16(m,6H),2.05-1.95(m,6H),1.89-1.81(m,6H), 1.34(s,18H),0.63(d,6H,J=6.7),0.55(d,6H,J=6.5Hz),0.14(s,6H).

[0217] Complex 21: Synthesis of [2',2"'-(4-[4-methyl-2,6,7-trioxabicyclo[2.2.2]octane-1-yl]pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)]dimethylzirconium To a pre-cooled stirred suspension of zirconium tetrachloride (25 mg, 0.11 mmol, 1 eq) in toluene (2 mL) was added a solution of methylmagnesium bromide (0.15 mL, 3.0 M in diethyl ether, 0.45 mmol, 4.2 eq). Then, a pre-cooled solution of 2',2"'-(4-(4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)-pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (99 mg, 0.11 mmol, 1 eq) in toluene (2 mL) was added. The reaction was stirred at room temperature for 19 hours. The reaction was concentrated at 50 °C under a stream of nitrogen and then placed under high vacuum. The product was concentrated under 40 ℃ of 5% ethanol. The residue was extracted with pentane (15 mL), then extracted with toluene (5 mL), and filtered on diatomaceous earth (Celite). The combined filtrate was collected and concentrated under a stream of nitrogen, and then concentrated under high vacuum. The residue was extracted with hot hexane and filtered on diatomaceous earth (Celite). The filtrate was cooled to -35 ℃, resulting in crystal precipitation. The colorless crystals were collected and concentrated under high vacuum to obtain the product as clear colorless crystals (52.1 mg, 46% yield). 1 H NMR (400MHz, C6D6): δ7.57 (d, 2H, J = 2.6Hz), 7.50 (s, 2H), 7.20-7.17 (m, 2H) ,7.10-7.02(m,4H),6.95(td,2H,J=7.5,1.3Hz),6.80(dd,2H,J=7.6,1.3Hz) ,3.34(s,6H),2.59-2.50(m,6H),2.45-2.36(m,6H),2.21-2.13(m,6H),2.0 5-1.95(m,6H),1.87-1.78(m,6H),1.34(s,18H),0.13(s,6H),-0.12(s,3H).

[0218] Complex 22 To a mixture of ZrCl4(Et2O)2 (55.0 mg, 0.144 mmol) and 2',2"'-(4-((p-tolyloxy)methyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (125 mg, 0.136 mmol) in toluene (~3 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.2 mL, 0.6 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 21 hours and then concentrated under vacuum to a solid.

[0219] Prophetic synthesis of complex 23 To a mixture of ZrCl4(Et2O)2 (55.0 mg, 0.144 mmol) and 2',2"'-(4-(n-butyldimethylsilyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (124 mg, .136 mmol) in toluene (~3 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.2 mL, 0.6 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 70 minutes and then evaporated to dryness. The resulting solid was extracted with isohexane (~10 mL total) and the combined extracts were filtered through Celite. The filtrate was then concentrated under vacuum to a solid which could subsequently be recrystallized from hexanes.

[0220] Complex 24: Synthesis of [2',2"'-(4-(((1S,2R,5S)-2-isopropyl-5-methylcyclohexyl)oxy)pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenolate)]dimethylzirconium To a pre-cooled stirred suspension of zirconium tetrachloride (49 mg, 0.21 mmol, 1 eq) in toluene (2 mL) was added methylmagnesium bromide (0.28 mL, 3.0 M in diethyl ether, 0.84 mmol, 4 eq). Then, a pre-cooled solution of 2',2"'-((4-(((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)oxy)pyridine)-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-phenol) (200 mg, 0.210 mmol) in toluene (2 mL) was added. The reaction was stirred at room temperature for 30 minutes. The reaction was concentrated under a nitrogen stream and then under high vacuum. The residue was extracted with hexanes (15 mL) and filtered over celite. The hexane extracts were concentrated under a nitrogen stream and then under high vacuum to give the product as a brown solid containing hexanes (0.69 equiv) (156 mg, 66% yield). 1H NMR (400MHz, C6D6): δ7.56 (d, 2H, J = 2.6Hz), 7.25-7.21 (m, 2H), 7.14-7.04 (m, 8H), 6.47 (d, 2H, J = 12.0Hz), 3.80-3.52 (m, 1H), 2.64-2.54 (m,6H),2.50-2.41(m,6H),2.23-2.15(m,6H),2.05-1.96 (m,6H),1.89-1.80(m,6H),1.39-1.30(m,24H),0.77-0.68(m,6H),0.57(d,2H,J=6.5Hz),0.52-0.44(m,4H),0.12(s,6H).

[0221] Complex 25: Synthesis of [2',2"'-(4-ethoxypyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)]dimethylzirconium To a pre-cooled stirred suspension of zirconium tetrachloride (24 mg, 0.10 mmol, 1 eq) in toluene (5 mL) was added methylmagnesium bromide (0.14 mL, 3.0 M in diethyl ether, 0.42 mmol, 4.2 eq). Then, a pre-cooled solution of 2',2"'-(4-ethoxypyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (84 mg, 0.10 mmol) in toluene was added. The reaction was stirred at room temperature for 1 hour. The reaction was concentrated under a stream of nitrogen while heating to 70°C and then concentrated under high vacuum. The residue was extracted with pentane (15 mL) and filtered over celite. The pentane extract was cooled to -35°C. The resulting precipitated colorless crystals were collected and concentrated under high vacuum to give the product as a white solid containing hexanes (1.14 eq) (39 mg, 37% yield). 1 H NMR (400MHz, C6D6): δ7.57(d,1H,J=2.6Hz),7.23-7.18(m,2H),7.13-7.07(m,8H),6.08(s,2H),2.89-2.73(m,2H),2.67-2.57(m,6 H),2.53-2.43(m,6H),2.25-2.16(m,6H),2.07-1.98(m,6H),1.90-1.81(m,6H),1.33(s,18H),0.66(t,3H,J=7.0Hz),0.14(s,6H).

[0222] Prophetic synthesis of complex 26 To a mixture of ZrCl4(Et2O)2 (55.0 mg, 0.144 mmol) and 2',2"'-(3-(n-butyldimethylsilyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (124 mg, 0.136 mmol) in toluene (~3 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.2 mL, 0.6 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 70 minutes and then evaporated to dryness. The resulting solid was extracted with methylcyclohexane (~10 mL total) and the combined extracts were filtered through Celite. The filtrate was then concentrated under vacuum to a solid.

[0223] Prophetic synthesis of complex 27 To a mixture of ZrCl4(Et2O)2 (55.0 mg, 0.144 mmol) and 2',2"'-(4-(hept-1-yn-1-yl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (121 mg, 0.136 mmol) in toluene (~3 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.2 mL, 0.6 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 70 minutes and then evaporated to dryness. The resulting solid was extracted with methylcyclohexane (~10 mL total) and the combined extracts were filtered through Celite. The filtrate was then concentrated under vacuum to a solid.

[0224] Prophetic synthesis of complex 28 To a mixture of ZrCl4(Et2O)2 (55.0 mg, 0.144 mmol) and 2',2"'-(4-(1,5-diazabicyclo[3.2.1]octan-8-yl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (124 mg, 0.136 mmol) in toluene (~3 mL) cooled at -40°C was added MeMgBr (3.0 M, 0.2 mL, 0.6 mmol) dropwise. The reaction mixture was stirred at ambient temperature for 70 minutes and then evaporated to dryness. The resulting solid was extracted with methylcyclohexane (~10 mL total) and the combined extracts were filtered through Celite. The filtrate was then concentrated under vacuum to a solid.

[0225] Complex 29: [2',2"'-(4-(pyrrolidin-1-yl)pyridine-2,6-diyl)bis(5-methyl-3-(3,5,7-trimethyladamantan-1-yl)-[1,1'-biphenyl]-2-phenol)]dimethylhafnium To a suspension of 111 mg (0.346 mmol) of hafnium tetrachloride in 40 ml of dry toluene at 0°C was added (via syringe) 540 μL (1.56 mmol) of 2.9 M MeMgBr in diethyl ether in one portion. To the resulting suspension was immediately added 300 mg (0.346 mmol) of 2',2"'-(4-(pyrrolidin-1-yl)pyridine-2,6-diyl)bis(5-methyl-3-(3,5,7-trimethyladamantan-1-yl)-[1,1'-biphenyl]-2-phenol in one portion. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The solid obtained was extracted with 2×20 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. 271 mg (73%) of a white solid was produced. 63 H 76 Anal. Calc. for HfN2O2: C, 70.60; H, 7.15; N, 2.61. Found: C 70.92; H, 7.37; N 2.94. 1 H NMR (C6D6, 400MHz): δ7.48(t,J=7.4Hz,2H),7.39(d,J=7.1Hz,2H),7.24-7.31(m,4H),7.00-7.02(m,2H),6.90(d,J=1.5Hz,2H),5.67(s,2H) ,2.24(s,6H),2.10-2.16(m,6H),1.93-2.04(m,10H),1.37-1.40(m,6 H),1.06-1.11(m,6H),1.03(s,18H),0.89-0.93(m,4H),-0.11(s,6H). 13 C NMR(C6D6,100MHz)δ160.7,157.4,143.9,138.4,134.7,133.8,133.4,130.8,130.1,129.7,12 9.4,129.2,128.9,126.3,126.0,107.3,51.2,50.8,47.3,46.6,40.9,32.9,31.6,24.7,21.8.

[0226] Complex 30: [2',2"'-(4-(pyrrolidin-1-yl)pyridine-2,6-diyl)bis(3-(3,5-dimethyladamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenol)]dimethylhafnium To a suspension of 96 mg (0.299 mmol) hafnium tetrachloride in 40 ml dry toluene at 0°C was added (via syringe) 470 μL (1.35 mmol) 2.9 M MeMgBr in diethyl ether in one portion. To the resulting suspension was immediately added 250 mg (0.301 mmol) of 2',2"'-(4-(pyrrolidin-1-yl)pyridine-2,6-diyl)bis(3-(3,5-dimethyladamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenol) in one portion. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The obtained solid was extracted with 2×20 mL of hot toluene, and the combined organic extracts were filtered through a thin pad of Celite 503. Further, 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. 219 mg (70%) of a white-beige solid was obtained. C 61 H 72 Calculated values ​​for HfN2O2: C, 70.20; H, 6.95; N, 2.68. Found: C 70.55; H, 7.04; N 2.87. 1 H NMR(C6D6,400MHz): δ7.29-7.40(m,6H),7.24-7.26(m,2H),7.01-7.03(m,2H) ,6.92(s,2H),5.66(s,2H),2.90-2.97(m,2H),2.80-2.85(m,2H),2.36(br.s, 2H),2.25(s,6H),1.88-1.98(m,10H),1.50-1.66(m,6H),1.36-1.40(m,2H),1 .19-1.27(m,6H),1.01(s,6H),0.99(s,6H),0.89-0.91(m,4H),-0.11(s,6H). 13C NMR(C6D6,100MHz)δ160.5,157.5,144.0,138.7,134.2,133.9,133.7,131.1,131.0,129.7,129.4,126.5 ,126.0,107.3,52.1,50.8,49.5,46.6,44.5,43.1,40.3,39.9,32.5,32.2,32.0,31.6,31.0,24.7,21.5. Complex solubility

[0227] General considerations: Solubility studies of complex 2 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 3 was isolated with 1 equivalent of pentane. Complex 4 was isolated with 0.18 equivalents of hexane and 0.96 equivalents of toluene. Complex 6 was isolated with 0.75 equivalents of pentane. Complex 8 was isolated with 0.5 equivalents of pentane. Complex 14 was isolated with 1 equivalent of isohexane. Complex 16 was isolated with 0.39 equivalents of toluene. Complex 20 was isolated with 2.63 equivalents of hexane and 0.28 equivalents of toluene. Complex 24 was isolated with 0.69 equivalents of hexane. Complex 25 was isolated with 1.14 equivalents of hexane. The 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°C-25°C).

[0228] 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.

[0229] Method 1: A tared vial is charged with a small amount of the complex (the actual mass recorded, including any residual solvent as described above, is typically 5-30 mg). Then, a small stirring bar (8 mm) is added. The solvent is then 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 an additional 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 solvent required to reach homogeneity. The stirring bar is then 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.

[0230] Method 2: A measured amount of the complex (actual mass recorded, including any residual solvent as described above) is added to a tared vial, followed by a stir bar. Dry isohexane is added in small portions and the resulting mixture is stirred after each addition of isohexane. If a clear solution has formed, the solubility is 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 is obtained. If the mixture remains heterogeneous (visible solids or turbidity), the upper limit of the solubility is calculated using the total solvent added. The formula for calculating the solubility is shown below. The solvent present in the complex is included in the mass and molecular weight (formula weight) of the complex.

[0231] Solubility (mM) = [10 6 ]×[(complex weight in grams) / (complex molecular weight, 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 [(complex weight) / (solution weight)]. Table 1. Solubility of selected complexes in isohexane at ambient temperature *Comparative complex Polymerization Example

[0232] 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 0.25 mmol / L.

[0233] 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.

[0234] 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).

[0235] 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.

[0236] 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:

[0237] 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 the reactor for C2 and C2 / C8 tests = 23.5 mL; for C3 tests = 22.5 mL), a septum inlet, regulated nitrogen, ethylene and propylene supplies and equipped with 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):

[0238] 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 about 50 psi of compressed dry air gas mixture 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. Polymer characterization

[0239] For analytical testing, polymer sample solutions were prepared in a shaker oven at 165°C 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) 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.

[0240] 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 5,000 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 instrument available from Symyx Technologies was used. Numerical analysis was performed using the Automaton software or Automation Studio software available from Freeslate. The molecular weights obtained were 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.

[0241] 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).

[0242] The polymerization results are collected in Table 2 below. "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 test in seconds. For propylene homopolymerization tests, the quenching value represents the maximum set pressure loss (conversion) of propylene (for PP tests) during polymerization. Activity is reported in grams of polymer / mmol catalyst / hour.

[0243] 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, with a 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, the procatalyst solution was in isohexane or toluene, and the activator solution was in toluene. When activator B was used, both the procatalyst and activator solutions were in isohexane. A small amount of methylcyclohexane was derived from activator B, which was provided by the manufacturer as a 10 wt % solution in methylcyclohexane.

[0244] Polymerization is also carried out in a continuous stirred tank reactor system. A 1-liter autoclave reactor is equipped with an agitator, a pressure controller, and a water-cooled / steam-heating element with a temperature controller. The reactor is operated at a reactor pressure exceeding the bubble point pressure of the reaction mixture in a liquid filling condition, thereby keeping the reactants in the liquid phase. Isohexane and propylene are pumped into the reactor by a Pulsa feed pump. All flow rates of the liquid are controlled using a Coriolis mass flow controller (Quantim series from Brooks). Ethylene flows through a Brooks flow controller as a gas under its own pressure. Ethylene and propylene feeds are combined into one stream and then mixed with a precooled isohexane stream that has been cooled to at least 0°C. The mixture is then supplied to the reactor via a single pipeline. A solution of tri(n-octyl)aluminum is added to the combined solvent and monomer stream that is about to enter the reactor. The catalyst solution is fed into the reactor via a separate pipeline using an ISCO injection pump.

[0245] Isohexane (used as solvent) and monomers (such as propylene and ethylene) are purified on alumina and molecular sieve beds. Toluene and isohexane used to prepare the catalyst solution are purified by the same technique.

[0246] The polymer produced in the reactor leaves through a back pressure control valve that reduces the pressure to atmospheric pressure. This flashes the unconverted monomers in the solution into a vapor phase that is discharged from the top of a vapor liquid separator. The liquid phase, which mainly comprises polymer and solvent, is collected to recover the polymer. The collected samples are first air-dried in a fume hood to evaporate most of the solvent and then dried in a vacuum oven at a temperature of about 90° C. for about 12 hours. The vacuum oven dried samples are weighed to obtain the yield. Unless otherwise stated, all reactions are carried out at a pressure of about 2.4 MPa / g.

[0247] Detailed polymerization process conditions and the physical properties of the produced polymers are listed in Table C1 below. Tetrakis (pentafluorophenyl) boric acid N, N-dimethylanilinium was used as an activator for all polymerizations. Catalyst solutions were prepared by combining the catalyst with the activator in toluene. Examples G01 to G06 are propylene-ethylene copolymers prepared from catalyst 6. Examples G07 to G11 are propylene-ethylene copolymers prepared from catalyst 15. Examples G12 to G13 are propylene-ethylene copolymers made from catalyst 14.

[0248] Ethylene content was determined using FTIR according to ASTM D3900.

[0249] The peak melting point Tm (also called melting point), the peak crystallization temperature Tc (also called crystallization temperature), and the glass transition temperature (Tg) and the heat of fusion (ΔHf or Hf) were determined using Differential Scanning Calorimetry (DSC) from TA Instruments (Model Q200) according to the procedure of ASTM D3418-03.

[0250] MFR is the melt flow rate in g / 10 min. measured according to ASTM D1238 at a temperature of 230° C. and a weight of 2.16 kg. HL MFR is the melt flow rate in g / 10 min. measured according to ASTM D1238 at a temperature of 230° C. and a weight of 21.6 kg. Table C1 Table C1 (continued) Table C1 (continued)

[0251] 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%.

[0252] 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.

[0253] 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 40 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 40 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 40 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 40 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 are optionally linked together to form a bidentate Lewis base; The X group is optionally linked to the L group to form a monoanionic bidentate group; and Any two X groups are optionally linked together to form a dianionic ligand group, The condition is R 17 , R 18 and R 19 At least one of the moieties contains at least two or more saturated or unsaturated carbon atoms.

2. The catalyst compound of claim 1, wherein R 18 or R 19 C2-C 40 Hydrocarbon, C2-C 40 Substituted hydrocarbon or C2-C 40 Containing heteroatom groups.

3. The catalyst compound of claim 1, wherein R 18 or R 19 A linear chain containing at least three non-hydrogen atoms in length and terminally bonded to pyridine.

4. The catalyst compound of claim 2, wherein the C2-C 40 The hydrocarbyl group is selected from the group consisting of ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl and isomers thereof.

5. The catalyst compound of claim 4, wherein the C2-C 40 The hydrocarbyl group is selected from ethyl, propyl, butyl, butenyl, hexynyl, butylphenyl and isomers thereof.

6. The catalyst compound of claim 2, wherein the C2-C 40 The substituted hydrocarbyl group is selected from the group consisting of hydrocarbylenetrihydrocarbylenesilane, hydrocarbylenetrihydrocarbylenegermane, (dihydrocarbylaminyl)hydrocarbylene, (dihydrocarbylphosphino)hydrocarbylene, (hydrocarbyloxy)hydrocarbylene and (hydrocarbylthio)hydrocarbylene.

7. The catalyst compound of claim 6, wherein the C2-C 40 The substituted hydrocarbon group is selected from methylenedimethylbutylsilane, methylenetriethylsilane, methylenetrihexylsilane, (dipropylamino)methylene, 1,5-diazabicyclo[3.2.1]octan-8-yl, 4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl, (tolyloxy)methylene and isomers thereof.

8. The catalyst compound of claim 2, wherein the C2-C 40 The heteroatom-containing group is selected from the group consisting of a hydrocarbyloxy group, a hydrocarbylthio group, a trihydrocarbylsilyl group, a trihydrocarbylgermyl group, a dihydrocarbylamino group and a dihydrocarbylphosphino group.

9. The catalyst compound of claim 8, wherein the C2-C 40 The heteroatom-containing group is selected from ethylthio, butylthio, dodecylthio, ethoxy, butoxy, phenoxy-4-(2,4,4-trimethylpentane-2-yl), (1R,2S,5R)-2-isopropyl-5-methylcyclohexane-1-oxy, pyrrolidinyl, dimethylbutylsilyl and isomers thereof.

10. The catalyst compound of claim 1, wherein R 4 and R 5 It is an adamantyl group or a substituted adamantyl group.

11. The catalyst compound of claim 1, wherein R 4 and R 5 is adamantyl or substituted adamantyl, R 18 Containing the formula A(R a )(R b )(R c ) 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.

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

13. A catalyst system comprising an activator, preferably a non-aromatic hydrocarbon, and optionally a support material, and a catalyst compound according to any preceding claim.

14. A homogeneous solution comprising: an aliphatic hydrocarbon solvent; and At least one catalyst compound of any one of claims 1-12, 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).

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

16. A process for producing a propylene-based or ethylene-based polymer or copolymer, comprising: Propylene, ethylene, or ethylene and 1-octene are polymerized by contacting propylene, ethylene, or ethylene and 1-octene with the catalyst system of claim 13 in one or more continuously stirred tank reactors or loop reactors connected in series or in 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 or copolymer.

17. The process of claim 16, wherein the catalyst system and the activator are fed separately into the one or more reactors.

18. The process of claim 16, wherein the catalyst system and the activator are premixed prior to feeding into the one or more reactors.

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