CN113614123A

CN113614123A - Transition metal bis (phenolate) complexes and their use as olefin polymerization catalysts

Info

Publication number: CN113614123A
Application number: CN202080023077.4A
Authority: CN
Inventors: G·P·戈于诺夫; M·I·夏利科夫; V·A·波波夫; D·V·乌博斯基; A·Z·沃斯科宾尼科夫; J·R·哈格多恩; M·E·蒂东尼; A·E·卡彭特; C·A·菲勒; J·A·M·卡尼奇
Original assignee: ExxonMobil Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2019-02-12
Filing date: 2020-02-11
Publication date: 2021-11-05
Anticipated expiration: 2040-02-11
Also published as: SG11202108252UA; JP7242879B2; WO2020167821A1; KR20210118204A; WO2020167799A1; EP3924395A1; CN113423742A; SG11202107809TA; JP2022520575A; EP3924394A4; CN113614123B; WO2020167824A1; EP3924394A1; CN113423742B; EP3924395A4

Abstract

The invention relates to transition metal complexes of dianionic tridentate ligands, characterised by a central neutral heterocyclic Lewis base and two phenoxide donors, wherein the tridentate ligand is coordinated to the metal centre to form two eight-membered rings. Superior foodOptionally, the bis (phenolate) complex is represented by the following formula (I):

wherein M, L, X, M, n, E', Q, R¹、R²、R³、R⁴、R¹'、R²'、R³'、R⁴'、A¹、A¹'、

And

as defined herein, wherein A¹QA¹' is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, which bridges A via a 3-atom bridge²Is connected to A²', wherein Q is the central atom of the 3-atom bridge.

Description

Transition metal bis (phenolate) complexes and their use as olefin polymerization catalysts

The inventor: georgy p. goryunov, Mikhail i.sharkov, vladillav a.popov, Dmitry v.uborsky, Alexander z.voskoboynikov, John r.hagadorn, Michelle e.titone, Alex e.carpenter, cathine a.faller, John m.canich

Priority

The present invention claims the benefits and priority of USSN 62/804,372 filed on 12.2.2019 and EP search report application No. 19179811.5 filed on 12.6.2019, the disclosures of which are incorporated herein in their entirety.

Technical Field

The present invention relates to novel catalyst compounds comprising group 4 bis (phenolate) complexes, catalyst systems comprising the same and uses thereof.

Background

Olefin polymerization catalysts have important applications in industry. Therefore, there is an interest in finding new catalyst systems that increase the commercial utility of the catalyst and allow the preparation of polymers with improved properties.

Catalysts for olefin polymerization may be based on bis (phenolate) complexes as catalyst precursors, which are typically activated by aluminoxanes or activators containing non-coordinating anions.

KR 2018022137(LG Chem.) describes transition metal complexes of bis (methylphenylphenoxide) pyridine.

US 7,030,256B 2(Symyx Technologies, Inc.) describes bridged bi-aromatic ligands, catalysts, polymerization processes, and polymers therefrom.

US 6,825,296(University of Hong Kong) describes transition metal complexes of bis (phenolate) ligands, which are coordinated to the metal with two 6-membered rings.

US 7,847,099(California Institute of Technology) describes transition metal complexes of bis (phenolate) ligands, which are coordinated to the metal with two 6-membered rings.

WO 2016/172110- (Univation Technologies) describes tridentate bis (phenolate) ligand complexes characterised by acyclic ether or thioether donors.

Other references of interest include: baier, M.C. (2014) "Post-metals in the Industrial Production of polyolfins," inlet.chem.int.ed.2014, v.53, pp.9722-9744; and Golisz, S.et al ((2009) "Synthesis of Early transfer Metal Bisphenolate Complexes and the third Use as Olefin Polymerization Catalysts," Macromolecules, v.42(22), pp.8751-8762.

New catalysts capable of polymerizing olefins at high process temperatures to produce high molecular weight and/or high tacticity polymers are desirable for the commercial production of polyolefins. There remains a need in the art for new and improved catalyst systems for olefin polymerization to achieve specific polymer properties, such as high molecular weight and/or high tacticity polymers, preferably at high process temperatures.

It is therefore an object of the present invention to provide novel catalyst compounds, catalyst systems comprising such compounds and processes for the polymerization of olefins using such compounds and systems.

Disclosure of Invention

The invention relates to transition metal complexes of dianionic tridentate ligands, characterised by a central neutral heterocyclic Lewis base and two phenoxide donors, wherein the tridentate ligand is coordinated to the metal centre to form two eight-membered rings.

The present invention relates to a bis (phenolate) complex represented by the following formula (I):

wherein:

m is a group 3-6 transition metal or a lanthanide;

e and E' are each independently O, S or NR⁹Wherein R is⁹Independently of one another is hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀A substituted hydrocarbyl or heteroatom-containing group;

q is a group 14, 15 or 16 atom that forms a coordinate bond with metal M;

A¹QA^1'is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, which connects A via a 3-atom bridge²Is connected to A^2'Wherein Q is the central atom of the 3-atom bridge, A¹And A¹' independently is C, N or C (R)²²) Wherein R is²²Selected from hydrogen, C₁-C₂₀Hydrocarbyl radical, C₁-C₂₀A substituted hydrocarbyl group;

is a divalent radical containing 2 to 40 non-hydrogen atoms which bridges A via a 2-atom¹An aryl group attached to the E bond;

is a divalent radical containing 2 to 40 non-hydrogen atoms which bridges A via a 2-atom¹'an aryl group linked to an E' linkage;

l is a neutral Lewis base;

x is an anionic ligand;

n is 1, 2 or 3;

m is 0, 1 or 2;

n + m is not more than 4;

R¹、R²、R³、R⁴、R¹'、R²'、R³' and R⁴Each of' is independently hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R¹And R²、R²And R³、R³And R⁴、R¹' and R²'、R²' and R³'、R³' and R⁴One or more pairs of' may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic or unsubstituted heterocyclic rings, each having 5, 6, 7 or 8 ring atoms, and wherein substituents on the rings may join to form additional rings;

Any two L groups may be joined together to form a bidentate lewis base;

the X group may be joined to the L group to form a monoanionic bidentate group;

any two X groups may be joined together to form a dianionic ligand group.

The invention also relates to a process for polymerizing olefins comprising contacting the catalyst compound described herein with an activator and one or more monomers. The invention also relates to polymer compositions prepared by the methods described herein.

Definition of

For the purposes of the present invention and its claims, the following definitions should be used.

The new numbering scheme for the groups of the periodic Table of the elements 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.

"catalyst productivity" is a measure of the amount of polymer mass produced using a known amount of polymerization catalyst. In general, "catalyst productivity" is expressed in units of (g polymer)/(g catalyst) or (g polymer)/(mmol catalyst) and the like. If no units are specified, "catalyst productivity" is in units of (g polymer)/(g catalyst). To calculate catalyst productivity, only the weight of the transition metal component of the catalyst is used (i.e., the activator and/or cocatalyst is omitted). "catalyst activity" is a measure of the amount of polymer mass produced per unit time for batch and semi-batch polymerizations using a known amount of polymerization catalyst. To calculate catalyst productivity, only the weight of the transition metal component of the catalyst is used (i.e., the activator and/or cocatalyst is omitted). In general, "catalyst activity" is expressed in units of (g polymer)/(mmol catalyst)/hour or (kg polymer)/(mmol catalyst)/hour, etc. If no units are specified, the units of "catalyst activity" are (g polymer)/(mmol catalyst)/hour.

"conversion" is the percentage of monomer converted to polymer product in the polymerization and is reported as% and is calculated based on polymer yield, polymer composition and amount of monomer fed to the reactor.

An "olefin," alternatively referred to as an "olefinic hydrocarbon," is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction and the derived units are present at 35 wt% to 55 wt% based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer comprising the same monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. A "terpolymer" is a polymer having three monomer units that differ from each other. Thus, the definition of copolymer as used herein includes terpolymers and the like. "different" as used in reference to a monomeric unit indicates that the monomeric units differ from each other by at least one atom or are isomerically different. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50 mole% ethylene derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50 mole% propylene derived units, and the like.

Ethylene should be considered an alpha-olefin.

Unless otherwise indicated, the term "Cn" refers to a hydrocarbon having n carbon atoms (one or more) per molecule, where n is a positive integer.

The term "hydrocarbon" refers to a class of compounds containing hydrogen bonded to carbon, and includes mixtures of (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different values of n. Likewise, "C_m-C_y"group or compound means a group or compound comprising carbon atoms in the total number of m to y. Thus, C₁-C₅₀Alkyl refers to alkyl groups containing carbon atoms in a total number of 1 to 50.

The terms "group," "radical," and "substituent" may be used interchangeably.

The terms "hydrocarbyl", "hydrocarbyl group", or "hydrocarbyl" are used interchangeablyUsed, and defined to mean a group consisting only of hydrogen and carbon atoms. Preferred hydrocarbyl is C₁-C₁₀₀A group, which may be linear, branched or cyclic, and when cyclic, may be aromatic or non-aromatic. Examples of such groups include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, aryl groups such as phenyl, benzyl, naphthyl, and the like.

Unless otherwise indicated (e.g., the definition of "substituted hydrocarbyl", etc.), the term "substituted" means that at least one hydrogen atom has been substituted with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom or a heteroatom-containing group, such as a halogen (e.g., Br, Cl, F or I) or at least one functional group, such as-NR ″₂，-OR*，-SeR*，-TeR*，-PR*₂，-AsR*₂，-SbR*₂，-SR*，-BR*₂，-SiR*₃，-GeR*₃，-SnR*₃，-PbR*₃，-(CH₂)_q-SiR*₃Etc., wherein q is 1 to 10, each R is independently hydrogen, a hydrocarbyl group, or a halocarbyl group, and two or more R may be joined 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 within the hydrocarbyl ring.

The term "substituted hydrocarbyl" refers to a hydrocarbyl group in which at least one hydrogen atom of the hydrocarbyl group has been replaced by at least one heteroatom (e.g., halogen, such as Br, Cl, F, or I) or heteroatom-containing group (e.g., a functional group, such as — NR;)₂、-OR*、-SeR*、-TeR*、-PR*₂、-AsR*₂、-SbR*₂、-SR*、-BR*₂、-SiR*₃、-GeR*₃、-SnR*₃、-PbR*₃、-(CH₂)_q-SiR*₃Etc., wherein q is 1 to 10, and each R is independently hydrogen, a hydrocarbyl group, or a halogenated hydrocarbyl group, and two or more R may be joined 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.

The term "aryl" or "aryl group" refers to an aromatic ring (typically consisting of 6 carbon atoms) and substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl refers to aryl groups 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. The term "aromatic" as used herein also refers to pseudo-aromatic heterocycles, which are heterocyclic substituents having similar properties and structure (near planar) as aromatic heterocyclic ligands, but by definition are not aromatic.

The term "substituted aromatic" refers to an aromatic radical having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

A "substituted phenate" is a phenate group in which at least one, two, three, four or five of the hydrogen atoms in the 2, 3, 4, 5 and/or 6 positions have been substituted by at least one non-hydrogen group, such as a hydrocarbyl, heteroatom or heteroatom-containing group, such as a halogen (e.g. Br, Cl, F or I) or at least one functional group, such as-NR₂、-OR*、-SeR*、-TeR*、-PR*₂、-AsR*₂、-SbR*₂、-SR*、-BR*₂、-SiR*₃、-GeR*₃、-SnR*₃、-PbR*₃、-(CH₂)_q-SiR*₃Etc., wherein q is 1 to 10, and each R is independently hydrogen, hydrocarbyl or halohydrocarbyl, and two or more R' S may be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), wherein position 1 is a phenoxide (Ph-O-, Ph-S-, and Ph-N (R ^) -group, wherein R ^ is hydrogen, C, and ₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom, or heteroatom-containing group). Preferably, the "substituted phenoxide" group in the catalyst compounds described herein is represented by the formula:

wherein R is¹⁸Is hydrogen, C₁-C₄₀Hydrocarbyl radicals (e.g. C)₁-C₄₀Alkyl) or C₁-C₄₀Substituted hydrocarbon radicals, hetero atoms, or hetero atom-containing radicals, E¹⁷Is oxygen, sulfur or NR¹⁷And R is¹⁷、R¹⁸、R¹⁹、R²⁰And R²¹Each of which is independently selected from hydrogen, C₁-C₄₀Hydrocarbyl radicals (e.g. C)₁-C₄₀Alkyl) or C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R¹⁸、R¹⁹、R²⁰And R²¹Are joined together to form C₄-C₆₂Cyclic or polycyclic ring structures, or combinations thereof, and the wavy line indicates the position at which the substituted phenoxide group forms a bond with the remainder of the catalyst compound.

An "alkyl-substituted phenoxide" is a phenoxide group in which at least one, two, three, four or five hydrogen atoms in the 2, 3, 4, 5 and/or 6 positions have been substituted by at least one alkyl group, for example C₁-C₄₀Or C is₂-C₂₀Or C is₃-C₁₂Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl (adamantyl), and the like, including substituted analogs thereof.

An "aryl-substituted phenoxide" is a phenoxide in which at least one, two, three, four or five hydrogen atoms in the 2, 3, 4, 5 and/or 6 positions have been substituted by at least one aryl group, for example C₁-C₄₀Or C is₂-C₂₀Or C is₃-C₁₂Aryl groups such as phenyl, 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2, 6-dimethylphenyl, mesityl (mesityl), 2-ethylphenyl, naphthyl, and the like, including substituted analogs thereof.

The term "ring atom" refers to an atom that is part of a cyclic ring structure. According to this definition, benzyl has 6 ring atoms and tetrahydrofuran has 5 ring atoms.

Heterocycles, also referred to as heterocycles, are rings having heteroatoms in the ring structure, as opposed to "heteroatom-substituted rings" in which the hydrogen on a ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocycle and 4-N, N-dimethylamino-phenyl is a heteroatom-substituted ring. Substituted heterocycle refers to a heterocycle having one or more hydrogen groups replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

Substituted hydrocarbyl rings refer to rings of carbon and hydrogen atoms in which 1 or more hydrogen groups are replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

For the purposes of this disclosure, with respect to catalyst compounds (e.g., substituted bis (phenoxide) catalyst compounds), the term "substituted" refers to hydrogen groups that have been substituted with a hydrocarbyl group, a heteroatom or a heteroatom-containing group, such as a halogen (e.g., Br, Cl, F or I) or at least one functional group such as-NR ″₂、-OR*、-SeR*、-TeR*、-PR*₂、-AsR*₂、-SbR*₂、-SR*、-BR*₂、-SiR*₃、-GeR*₃、-SnR*₃、-PbR*₃、-(CH₂)_q-SiR*₃Etc., wherein q is 1-10, and each R is independently hydrogen, a hydrocarbyl group, or a halogenated hydrocarbyl group, and two or more R may be joined 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 within the hydrocarbyl ring.

Tertiary hydrocarbyl groups have a carbon atom bonded to three other carbon atoms. When the hydrocarbyl group is an alkyl group, the tertiary hydrocarbyl group is also referred to as a tertiary alkyl group. Examples of tertiary hydrocarbon groups include t-butyl, 2-methylbutan-2-yl, 2-methylhexan-2-yl, 2-phenylpropan-2-yl, 2-cyclohexylpropan-2-yl, 1-methylcyclohexyl, 1-adamantyl, bicyclo [2.2.1] heptan-1-yl, and the like. The tertiary hydrocarbyl group may be represented by formula a:

wherein R is^A、R^BAnd R^CAre hydrocarbyl or substituted hydrocarbyl groups which may optionally be bonded to each other, and the wavy line indicates the position at which the tertiary hydrocarbyl group forms a bond with other groups.

A cyclic tertiary hydrocarbon group is defined as a tertiary hydrocarbon group that forms at least one alicyclic (non-aromatic) ring. The cyclic tertiary hydrocarbon group is also referred to as an alicyclic tertiary hydrocarbon group. When the hydrocarbyl group is an alkyl group, the cyclic tertiary hydrocarbyl group is also referred to as a cyclic tertiary alkyl group or an alicyclic tertiary alkyl group. Examples of the cyclic tertiary hydrocarbon group include 1-adamantyl, 1-methylcyclohexyl, 1-methylcyclopentyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclododecyl, bicyclo [3.3.1] nonan-1-yl, bicyclo [2.2.1] heptan-1-yl, bicyclo [2.3.3] hexan-1-yl, bicyclo [1.1.1] pentan-1-yl, bicyclo [2.2.2] octan-1-yl and the like. The cyclic tertiary hydrocarbyl group may be represented by formula B:

Wherein R is^AIs a hydrocarbyl or substituted hydrocarbyl radical, each R^DIndependently is hydrogen or hydrocarbyl or substituted hydrocarbyl, w is an integer from 1 to about 30, R^AAnd one or more R^DAnd/or two or more R^DMay optionally be bonded to each other to form additional rings.

When the cyclic tertiary hydrocarbon group contains more than one cycloaliphatic ring, it may be referred to as polycyclic tertiary hydrocarbon group, or polycyclic tertiary alkyl group if the hydrocarbon group is alkyl.

The terms "alkyl group" and "alkyl" are used interchangeably throughout this disclosure. For purposes of this disclosure, "alkyl" is defined as C which may be linear, branched or cyclic₁-C₁₀₀An alkyl group. Examples of such groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including substituted analogs thereof. Substituted alkyl is where at least one hydrogen atom of the alkyl group has been replaced by at least one non-hydrogen group such as a hydrocarbyl group, a heteroatom or a heteroatom-containing group such as halogen (e.g., Br, Cl, F or I) orAt least one functional group, e.g. -NR₂、-OR*、-SeR*、-TeR*、-PR*₂、-AsR*₂、-SbR*₂、-SR*、-BR*₂、-SiR*₃、-GeR*₃、-SnR*₃、-PbR*₃、-(CH₂)_q-SiR*₃Etc., wherein q is 1-10 and each R is independently hydrogen, hydrocarbyl or halohydrocarbyl. 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 within the hydrocarbyl ring.

Where isomers of the alkyl, alkenyl, alkoxy, or aryl groups (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl) are present, reference to one member of the group (e.g., n-butyl) shall expressly disclose the remaining isomers in the family (e.g., isobutyl, sec-butyl, and tert-butyl). Likewise, reference to alkyl, alkenyl, alkoxy, or aryl without specifying a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

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 weight percent, and mol% is mole percent. Molecular Weight Distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol (g mol)^-1)。

The following abbreviations may be used herein: me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is n-butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, MAO is methylaluminoxane, dme is 1, 2-dimethoxyethane, p-tBu is p-tert-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOA and TNOAL are tri (n-octyl) aluminum, p-Me is p-methyl, Bn is benzyl (i.e., CH is methyl, n is ethyl, n is propyl, cPr is cyclopropyl, iBu is n-propyl, iPr is n-butyl, m is n-butyl, p-t-butyl is n-butyl, p-t-butyl is tri-t-butyl aluminum, TNOA and TNOAL is tri-t-butyl aluminum ₂Ph), THF (also known as THF) is tetrahydrofuran, RT is room temperature (and 23 ℃ unless otherwise stated), tol is toluene, EtOAc is ethyl acetateEster, Cbz is carbazole and Cy is cyclohexyl.

A "catalyst system" is a combination comprising at least one catalyst compound and at least one activator. When "catalyst system" is used to describe such a pairing prior to activation, it refers to the unactivated catalyst complex (procatalyst) along with the activator and optional co-activator. When it is used to describe such pairing after activation, it refers to the activated complex and the activator or other charge-balancing moiety. The transition metal compound may be neutral, as in the procatalyst, or a charged species with a counterion, as in the activated catalyst system. For purposes of the present invention and for purposes of the claims thereto, when the catalyst system is described as comprising components in a neutral stable form, it is well understood by those of ordinary skill in the art that the ionic form of the components is the form that reacts with the monomers to produce the polymer. Polymerization catalyst systems are catalyst systems that can polymerize monomers into polymers.

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

An "anionic ligand" is a negatively charged ligand that donates one or more electron pairs to a metal ion. The term "anion donor" is used interchangeably with "anionic ligand". In the context of the present invention, examples of anion donors include, but are not limited to, methyl, chloride, fluoride, alkoxy, aryloxy, alkyl, alkenyl, thiolate, carboxylate, amino (amidi), methyl, benzyl, hydride (hydrido), amidinate, and phenyl. Two anion donors can be joined to form a dianionic group.

A "neutral lewis base" or "neutral donor group" is an uncharged (i.e., neutral) group that donates one or more pairs of electrons to a metal ion. Non-limiting examples of neutral lewis bases include ethers, thioethers, amines, phosphines, diethyl ether, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, alkenes, alkynes, allene, and carbenes. The lewis base may be joined together to form a bidentate or tridentate lewis base.

For the purposes of the present invention and the appended claims, phenate donors include Ph-O-, Ph-S-, and Ph-N (R ^) groups, where R ^ is hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀A substituted hydrocarbyl, heteroatom or heteroatom-containing group, and Ph is an optionally substituted phenyl group.

Detailed Description

The present invention relates to a new catalyst family comprising transition metal complexes of dianionic tridentate ligands, characterized by a central neutral donor group and two phenoxide donors, wherein the tridentate ligands coordinate to the metal center to form two eight-membered rings. In this type of complex, it is advantageous for the central neutral donor to be a heterocyclic group. Heterocyclic groups are particularly advantageous in that they lack a hydrogen in the alpha position to the heteroatom. In this type of complex, it is also advantageous for the phenoxide to be substituted by one or more cyclic tertiary alkyl substituents. The use of cyclic tertiary alkyl substituted phenates has been shown to improve the ability of these catalysts to prepare high molecular weight polymers.

Complexes of substituted bis (phenolate) ligands, such as adamantyl substituted bis (phenolate) ligands, have been prepared and characterized herein. These complexes form active olefin polymerization catalysts when combined with an activator, such as a non-coordinating anion or alumoxane activator. Useful bis (arylphenolate) pyridine complexes comprise a tridentate bis (arylphenolate) pyridine ligand coordinated to a group 4 transition metal to form two eight-membered rings.

The invention also relates to a metal complex comprising: a metal selected from group 3-6 or lanthanide metals, and a tridentate dianionic ligand containing two anion donor groups and a neutral lewis base donor, wherein the neutral lewis base donor is covalently bonded between the two anion donors, and wherein the metal-ligand complex is characterized by a pair of 8-membered metal cyclide (metallocycle) rings.

The present invention relates to catalyst systems comprising an activator and one or more of the catalyst compounds described herein.

The invention also relates to a process for polymerizing olefins using the catalyst compounds described herein, comprising contacting one or more olefins with a catalyst system comprising an activator and the catalyst compounds described herein.

The present disclosure also relates to catalyst systems comprising a transition metal compound and an activator compound as described herein, to the use of such activator compounds for activating a transition metal compound in a catalyst system for polymerizing olefins, and to a process for polymerizing olefins comprising contacting one or more olefins under polymerization conditions with a catalyst system comprising a transition metal compound and an activator compound, wherein an aromatic solvent, such as toluene, is absent (present at zero mol% or present at less than 1 mol% relative to the moles of the activator, preferably the catalyst system, polymerization reaction, and/or polymer produced is free of "detectable aromatic hydrocarbon solvent", e.g., toluene). For purposes of this disclosure, "detectable aromatic hydrocarbon solvent" refers to 0.1mg/m as determined by gas chromatography ²Or more. For purposes of this disclosure, "detectable toluene" refers to 0.1mg/m as determined by gas chromatography²Or more.

The polyalphaolefins produced herein preferably contain 0ppm (or less than 1ppm, or less than 2ppm, or less than 5ppm) residual aromatic hydrocarbons. Preferably, the polyalphaolefins produced herein contain 0ppm (or less than 1ppm) residual toluene.

The catalyst system used here preferably contains 0ppm (or less than 1ppm) of residual aromatic hydrocarbons. Preferably, the catalyst system used herein contains 0ppm (or less than 1ppm) of residual toluene.

The polyalphaolefins produced herein preferably contain 5 wt% or less aromatic hydrocarbon, such as toluene, (alternatively, 4 wt% or less, alternatively, 3 wt% or less, alternatively, 2 wt% or less, alternatively, 1 wt% or less, alternatively, 0.5 wt% or less, alternatively, less than 50ppm, alternatively, less than 5ppm) residual aromatic hydrocarbon, such as toluene.

Catalyst compound

The terms "catalyst," "compound," "catalyst compound," and "complex" are used interchangeably to describe a transition metal or lanthanide metal complex that, when combined with a suitable activator, forms an olefin polymerization catalyst.

The catalyst complex of the present invention comprises a metal selected from the group consisting of group 3, 4, 5 or 6 or lanthanide metals of the periodic table of elements, a tridentate dianionic ligand comprising two anion donor groups, and a neutral heterocyclic lewis base donor, wherein the heterocyclic donor is covalently bonded between the two anion donors. Preferably, the dianionic tridentate ligand is characterized by a central heterocyclic donor group and two phenoxide donors, and the tridentate ligand is coordinated to the metal center to form two eight-membered rings.

The metal is preferably selected from group 3, 4, 5 or 6 elements. Preferably, the metal M is a group 4 metal. Most preferably, the metal M is zirconium or hafnium.

Preferably, the heterocyclic lewis base donor is characterized by a nitrogen or oxygen donor atom. Preferred heterocyclic groups include pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, and,

Derivatives of oxazole, thiazole, furan and substituted variants thereof. Preferably, the heterocyclic lewis base lacks hydrogen(s) in the alpha position to the donor atom. Particularly preferred heterocyclic lewis base donors include pyridine, 3-substituted pyridine and 4-substituted pyridine.

The anion donor of the tridentate dianionic ligand may be an arylthiolate (aryl thiolate), a phenoxide (phenoxide) or an anilide (anilide). The preferred anion donor is phenolate. Preferably, the tridentate dianionic ligand coordinates to the metal center to form a complex that lacks a symmetric mirror plane. Preferably, the tridentate dianionic ligand coordinates to the metal center to form a complex with two axes of symmetry; when determining the symmetry of the bis (phenolate) complex, only the metal and dianionic tridentate ligands are considered (i.e. the remaining ligands are ignored).

The bis (phenolate) ligands useful in the present invention are preferably tridentate dianionic ligands, which form a pair of 8-membered metallocyclate rings In such a way as to coordinate with the metal M. The bis (phenolate) ligand is wrapped around the metal to form a complex with a 2-fold axis of rotation, giving the complex a C₂Symmetry. C₂The geometry and 8-membered metallocycle rings are characteristic of these complexes, making them effective catalyst components for the production of polyolefins, particularly isotactic poly (alpha-olefins). If the ligand has a mirror surface in complex form (C)_s) The symmetry is coordinated to the metal in such a way that the catalyst is expected to produce only atactic poly (alpha-olefins); these symmetry-reactivity rules are summarized by Bercaw, j.e. (2009) in Macromolecules, v.42, pp.8751-8762. Said pair of 8-membered metallocyclate rings of the complexes of the invention is also a significant feature that is advantageous for the catalytic activity, the temperature stability and the isoselectivity of the monomer linkage (isomerization). Related group 4 complexes (Macromolecules 2009, 42, 8751-8762) characterized by smaller 6-membered metallated rings are known to form C when used in olefin polymerization₂And C_sMixtures of symmetric complexes, and are therefore less suitable for producing highly isotactic poly (alpha-olefins).

The bis (phenolate) ligands of the present invention containing an oxygen donor group (i.e. E ═ oxygen in formula (I)) are preferably substituted with alkyl, substituted alkyl, aryl or other groups. Advantageously, each phenoxide group is substituted at a ring position adjacent to the oxygen donor atom. Preferably, the substitution at the position adjacent to the oxygen donor atom is an alkyl group having 1 to 20 carbon atoms. Preferably, the substitution at the position immediately adjacent to the oxygen donor atom is a non-aromatic cyclic alkyl group having one or more five or six membered rings. Preferably, the substitution at the position immediately adjacent to the oxygen donor atom is a cyclic tertiary alkyl group. It is highly preferred that the substitution at the position immediately adjacent to the oxygen donor atom is adamantan-1-yl or substituted adamantan-1-yl.

The neutral heterocyclic lewis base donor is covalently bonded between the two anion donors via a "linking group" that connects the heterocyclic lewis base to the phenolate group. In formula (I), "linking group" is represented by (A)³A²) And (A)^2'A^3') And (4) showing. The choice of each linker can affect catalyst performance, for exampleSuch as the tacticity of the poly (alpha-olefin) produced. Each linker is typically C of two atoms in length₂-C₄₀A divalent group. One or both linkers may independently be phenylene, substituted phenylene, heteroaryl, vinylene, or an acyclic two carbon length linker. When one or both of the linking groups is phenylene, the alkyl substituents on the phenylene groups can be selected to optimize catalyst performance. Typically, one or two phenylene groups may be unsubstituted or may be independently substituted with C₁-C₂₀Alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl or isomers thereof, such as isopropyl, and the like.

The present invention also relates to catalyst compounds represented by formula (I) and catalyst systems comprising such compounds:

Wherein:

m is a group 3, 4, 5 or 6 transition metal or lanthanide (e.g., Hf, Zr, or Ti);

e and E' are each independently O, S or NR⁹Wherein R is⁹Independently of each other is hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl or heteroatom containing group, preferably O, preferably both E and E' are O;

q is a group 14, 15 or 16 atom that forms a coordinate bond with metal M, preferably Q is C, O, S or N, more preferably Q is C, N or O, most preferably Q is N;

A¹QA¹' is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, which bridges A via a 3-atom bridge²Is connected to A²', wherein Q is the central atom of the 3-atom bridge (A)¹QA¹' with connection A¹And A¹The combination of the curves for ` denotes a heterocyclic Lewis base), A¹And A¹' independently is C, N or C (R)²²) Wherein R is²²Selected from hydrogen, C₁-C₂₀Hydrocarbyl and C₁-C₂₀A substituted hydrocarbyl group. Preferably A¹And A¹' is C;

is a divalent radical containing 2 to 40 non-hydrogen atoms which bridges A via a 2-atom¹Aryl groups bound to E, e.g. ortho-phenylene, substituted ortho-phenylene, ortho-arene, indoleene (indoline), substituted indoleene, benzothiophene, substituted benzothiophene, pyrrolene (pyrrolene), substituted pyrrolene, thiophene, substituted thiophene, 1, 2-ethylene (-CH)₂CH₂-), substituted 1, 2-ethylene, 1, 2-ethenylene (-HC. CH-) or substituted 1, 2-ethenylene, preferably

Is a divalent hydrocarbon group;

is a divalent radical containing 2 to 40 non-hydrogen atoms which bridges A via a 2-atom¹Aryl 'linked to an E' linkage, e.g. ortho-phenylene, substituted ortho-phenylene, ortho-arene, indoleene, substituted indoleene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1, 2-ethylene (-CH)₂CH₂-), substituted 1, 2-ethylene, 1, 2-ethenylene (-HC. CH-) or substituted 1, 2-ethenylene, preferably

Is a divalent hydrocarbon group;

each L is independently a lewis base;

each X is independently an anionic ligand;

n is 1,2 or 3;

m is 0, 1 or 2;

n + m is not more than 4;

R¹、R²、R³、R⁴、R^1'、R^2'、R^3'and R^4'Each of which is independently hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group (preferably R)^1'And R¹Independently a cyclic group, e.g. cyclic tertiary alkyl), or R¹And R²、R²And R³、R³And R⁴、R^1'And R^2'、R^2'And R^3'、R^3'And R^4'One or more pairs of (a) may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic or unsubstituted heterocyclic rings, each having 5, 6, 7 or 8 ring atoms, and wherein substituents on the rings may join to form additional rings;

Any two L groups may be joined together to form a bidentate lewis base;

the X group may be joined to the L group to form a monoanionic bidentate group;

any two X groups may be joined together to form a dianionic ligand group.

The present invention further relates to catalyst compounds represented by formula (II) and catalyst systems comprising such compounds:

wherein:

m is a group 3, 4, 5 or 6 transition metal or lanthanide (e.g., Hf, Zr, or Ti);

each L is independently a lewis base;

each X is independently an anionic ligand;

n is 1, 2 or 3;

m is 0, 1 or 2;

n + m is not more than 4;

Any two L groups may be joined together to form a bidentate lewis base;

the X group may be joined to the L group to form a monoanionic bidentate group;

any two X groups may be joined together to form a dianionic ligand group;

R⁵、R⁶、R⁷、R⁸、R⁵'、R⁶'、R⁷'、R⁸'、R¹⁰、R¹¹and R¹²Each of which is independently hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R⁵And R⁶、R⁶And R⁷、R⁷And R⁸、R⁵' and R⁶'、R⁶' and R⁷'、R⁷' and R⁸'、R¹⁰And R¹¹Or R¹¹And R¹²May be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heteroringsRings, each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may join to form additional rings.

The metal M is preferably an element of group 3, 4, 5 or 6, more preferably group 4. Most preferably, the metal M is zirconium or hafnium.

The donor atom Q of the neutral heterocyclic Lewis base (in formula (I)) is preferably nitrogen, carbon or oxygen. Preferably, Q is nitrogen.

Non-limiting examples of neutral heterocyclic Lewis base groups include pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, and,

Derivatives of oxazole, thiazole, furan and substituted variants thereof. Preferred heterocyclic lewis bases include derivatives of pyridine, pyrazine, thiazole and imidazole.

Each A of heterocyclic Lewis bases (in formula I)¹And A¹' independently is C, N or C (R)²²) Wherein R is²²Selected from hydrogen, C₁-C₂₀Hydrocarbyl and C₁-C₂₀A substituted hydrocarbyl group. Preferably A¹And A^1′Is carbon. When Q is carbon, A is preferred¹And A^1′Selected from nitrogen and C (R)²²). When Q is nitrogen, A is preferred¹And A^1′Is carbon. Preferably Q ═ nitrogen, A¹＝A^1′Carbon. When Q is nitrogen or oxygen, it is preferred that the heterocyclic Lewis base in formula (I) does not have any bond with A¹Or A¹' an atom-bonded hydrogen atom. This is preferred because it is believed that hydrogen at those locations may undergo undesirable decomposition reactions that reduce the stability of the catalytically active material.

From A¹QA¹' with connection A¹And A¹The heterocyclic Lewis base (of formula I) represented by the combination of the curves of' is preferably selected from the following, wherein each R is²³The radicals being selected from hydrogen, hetero atoms, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy radical, C₁-C₂₀Amino (amide) and C₁-C₂₀A substituted alkyl group.

In some embodiments, from A¹QA¹' with connection A¹And A¹A heterocyclic Lewis base (of formula (I)) represented by the combination of the curves of' is a six-membered ring containing one ring heteroatom, wherein Q is a ring heteroatom, or a five-membered ring containing one or two ring heteroatoms, wherein Q is a ring carbon. Or, from A¹QA¹' with connection A¹And A¹A heterocyclic Lewis base (of formula (I)) represented by the combination of the curves of' is not a five-membered ring containing one or more ring heteroatoms, wherein Q is a ring heteroatom.

In formula (I) or (II), E and E' are each selected from oxygen or NR⁹Wherein R is⁹Independently of one another is hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl or heteroatom containing groups. Preferably E and E' are oxygen. When E and/or E' is NR⁹When, R is preferred⁹Is selected from C₁-C₂₀Hydrocarbyl, alkyl or aryl. In one embodiment, E and E' are each selected from O, S or N (alkyl) or N (aryl), wherein alkyl is preferably C₁To C₂₀Alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl and the like, and aryl is C₆To C₄₀Aryl groups such as phenyl, naphthyl, benzyl, methylphenyl, and the like.

In an embodiment of the present invention, the substrate is,

and

independently of one another, is a divalent hydrocarbon radical, e.g. C₁-C₁₂A hydrocarbyl group.

In the complexes of the formula (I) or (II), when E and E' are oxygen, it is advantageous for each phenoxide group to be in the immediate vicinity of the oxygen atom (i.e.R in the formula (I) or (II))¹And R¹') is substituted. Thus, when E and E' areWhen oxygen is present, R is preferred¹And R¹' Each of which is independently C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, more preferably R¹And R¹' each is independently a non-aromatic cyclic alkyl group having one or more five or six membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl or 1-methylcyclohexyl or substituted adamantyl), most preferably a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl or substituted adamantyl).

In some embodiments of formula (I) or (II) of the present invention, R¹And R¹Each of' is independently a tertiary hydrocarbon group. In other embodiments of formula (I) or (II) of the present invention, R¹And R¹Each of' is independently a cyclic tertiary hydrocarbon group. In other embodiments of formula (I) or (II) of the present invention, R¹And R¹Each of' is independently a polycyclic tertiary hydrocarbon group.

Linking group (i.e. of formula (I))

And

) Each is preferably ortho-phenylene, preferably part of substituted ortho-phenylene. R of the formula (II) is preferred⁷And R⁷The' position being hydrogen, or C₁-C₂₀Alkyl radicals, such as the methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecylAlkyl, octadecyl, nonadecyl, eicosyl, or isomers thereof, such as isopropyl, and the like. For applications targeting polymers with high tacticity, R of formula (II) is preferred ⁷And R⁷' position is C₁-C₂₀Alkyl, most preferably R⁷And R⁷' all are C₁-C₃An alkyl group.

In the embodiments of formula (I) herein, Q is C, N or O, preferably Q is N.

In the embodiments of formula (I) herein, A¹And A¹' independently is carbon, nitrogen or C (R)²²) Wherein R is²²Selected from hydrogen, C₁-C₂₀Hydrocarbyl radical, C₁-C₂₀A substituted hydrocarbyl group. Preferably A¹And A^1′Is carbon.

In the embodiments of formula (I) herein, A in formula (I)¹QA¹' is a heterocyclic Lewis base, e.g. pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene,

A moiety of an azole, thiazole, furan or substituted variant thereof.

In the embodiments of formula (I) herein, A¹QA¹' is part of a heterocyclic Lewis base containing 2 to 20 non-hydrogen atoms, which bridges A via a 3-atom bridge²Is connected to A²', wherein Q is the central atom of the 3-atom bridge. Preferably, each A¹And A¹' is a carbon atom, and A¹QA¹' fragment form is pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene,

A substituted variant of an azole, thiazole, furan or group thereof or a part of a substituted variant thereof.

In one embodiment of formula (I) herein, Q is carbon, and each A is¹And A¹' is N or C (R)²²) Wherein R is²²Selected from hydrogen, C₁-C₂₀Hydrocarbyl radical, C₁-C₂₀Substituted hydrocarbyl, heteroatom, or heteroatom-containing group. In this embodiment, A ¹QA¹' fragments are formed as part of a cyclic carbene, an N-heterocyclic carbene, a cyclic aminoalkyl carbene or a substituted variant of a group thereof or a substituted variant thereof.

In the embodiment of formula (I) herein,

is a divalent radical containing 2 to 20 non-hydrogen atoms which bridges A via a 2-atom¹To an E-bonded aryl group, wherein

Is a linear alkyl group or forms part of a cyclic group (e.g. an optionally substituted ortho-phenylene or ortho-arylene group) or a substituted variant thereof.

Is a divalent radical containing 2 to 20 non-hydrogen atoms which bridges A via a 2-atom¹Aryl 'linked to an E' bond, wherein

In embodiments of the invention herein, in formulas (I) and (II), M is a group 4 metal, such as Hf or Zr.

In embodiments of the invention herein, in formulae (I) and (II), E and E' are O.

In embodiments of the invention herein, in formulae (I) and (II), R¹、R²、R³、R⁴、R¹'、R²'、R³' and R⁴' independently is hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R¹And R²、R²And R³、R³And R⁴、R¹' and R²'、R²' and R³'、R³' and R⁴One or more pairs of' may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic or unsubstituted heterocyclic rings, each having 5, 6, 7 or 8 ring atoms, and wherein substituents on the rings may join to form additional rings, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof.

In embodiments of the invention herein, in formulae (I) and (II), R¹、R²、R³、R⁴、R¹'、R²'、R³'、R⁴' and R⁹Independently selected from the group consisting of methyl, 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, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

In embodiments of the invention herein, in formulae (I) and (II), R⁴And R⁴' independently is hydrogen or C₁-C₃Hydrocarbyl groups such as methyl, ethyl or propyl.

In embodiments of the invention herein, in formulae (I) and (II), R⁹Is hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbon radicals or heteroatom-containing radicals, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or isomers thereof. Preferably, R ⁹Is methyl, ethyl, propyl, butyl, C₁-C₆Alkyl, phenyl, 2-methylphenyl, 2, 6-dimethylphenyl or 2,4, 6-trimethylphenyl.

In embodiments of the invention herein, in formulas (I) and (II), each X is independently selected from hydrocarbyl (e.g., alkyl or aryl), hydride (hydride), amino (amide), alkoxy (alkoxide), thio (sulfide), phosphido (phosphide), halo (halide), alkylsulfonate (alkylsulfonate), and combinations thereof (two or more xs may form part of a fused ring or ring system) having from 1 to 20 carbon atoms, preferably, each X is independently selected from halo, aryl, and C₁-C₅Alkyl, preferably each X is independently hydrogen, dimethylamino, diethylamino, methyltrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl. Fluoro, iodo, bromo or chloro.

Alternatively, each X may independently be a halo, hydrogen, alkyl, alkenyl, or aralkyl group.

In embodiments of the invention herein, in formulas (I) and (II), each L is a lewis base independently selected from ethers, thioethers, amines, nitriles, imines, pyridines, halogenated hydrocarbons and phosphines, preferably ethers and thioethers and combinations thereof, optionally two or more L may form part of a fused ring or ring system, preferably each L is independently selected from ether and thioether groups, preferably each L is an ether, tetrahydrofuran, dibutyl ether or dimethyl thioether group.

In embodiments of the invention herein, in formulae (I) and (II), R¹And R¹' is independently a cyclic tertiary alkyl group.

In embodiments of the invention herein, in formulae (I) and (II), n is 1, 2 or 3, typically 2.

In the embodiments of the invention herein, in formulae (I) and (II), m is 0, 1 or 2, usually 0.

In embodiments of the invention herein, in formulae (I) and (II), R¹And R¹' is not hydrogen.

In the embodiments of the present invention herein, in the formulae (I) and (II), M is Hf or Zr, E and E' are O; r¹And R¹' Each of which is independently C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, each R²、R³、R⁴、R²'、R³' and R⁴' independently is hydrogen, C₁-C₂₀Hydrocarbyl radical, C₁-C₂₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R¹And R²、R²And R³、R³And R⁴、R¹' and R²'、R²' and R³'、R³' and R⁴One or more pairs of' may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may join to form additional rings; each X is independently selected from hydrocarbyl groups having 1 to 20 carbon atoms (e.g., alkyl or aryl), hydride, amino, alkoxy, thio, phosphorus, halo, and combinations thereof (two or more X may form part of a fused ring or ring system); each L is independently selected from ethers, thioethers, and halocarbons (two or more L may form a fused ring or part of a ring system).

In an embodiment of the invention herein, in formula (II), R⁵、R⁶、R⁷、R⁸、R⁵'、R⁶'、R⁷'、R⁸'、R¹⁰、R¹¹And R¹²Each of which is independently hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, or one or more adjacent R groups may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic or unsubstituted heterocyclic rings, each having 5, 6, 7 or 8 ring atoms, and wherein substituents on the rings may join to form additional rings.

In an embodiment of the invention herein, in formula (II), R⁵、R⁶、R⁷、R⁸、R⁵'、R⁶'、R⁷'、R⁸'、R¹⁰、R¹¹And R¹²Each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or isomers thereof.

In an embodiment of the invention herein, in formula (II), R⁵、R⁶、R⁷、R⁸、R⁵'、R⁶'、R⁷'、R⁸'、R¹⁰、R¹¹And R¹²Each of which is independently selected from the group consisting of methyl, 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, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

In the embodiments of the present invention herein, in formula (II), M is Hf or Zr, E and E' are O; r¹And R¹' Each of which is independently C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, each R¹、R²、R³、R⁴、R¹'、R²'、R³' and R⁴' independently is hydrogen, C₁-C₂₀Hydrocarbyl radical, C₁-C₂₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R¹And R²、R²And R³、R³And R⁴、R¹' and R²'、R²' and R³'、R³' and R⁴One or more pairs of' may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic or unsubstituted heterocyclic rings, each having 5, 6, 7 or 8 ring atoms, and wherein substituents on the rings may join to form additional rings; r⁹Is hydrogen,C₁-C₂₀Hydrocarbyl radical, C₁-C₂₀Substituted hydrocarbon groups or heteroatom-containing groups such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or isomers thereof;

each X is independently selected from hydrocarbyl groups having 1 to 20 carbon atoms (e.g., alkyl or aryl), hydride, amino, alkoxy, thio, phosphido, halo, diene, amine, phosphine, ether, and combinations thereof (two or more X's may form part of a fused ring or ring system); n is 2; m is 0; and R is⁵、R⁶、R⁷、R⁸、R⁵'、R⁶'、R⁷'、R⁸'、R¹⁰、R¹¹And R¹²Each of which is independently hydrogen, C ₁-C₂₀Hydrocarbyl radical, C₁-C₂₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, or one or more adjacent R groups may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic or unsubstituted heterocyclic rings, each having 5, 6, 7 or 8 ring atoms, and wherein substituents on the rings may join to form additional rings, e.g., R⁵、R⁶、R⁷、R⁸、R⁵'、R⁶'、R⁷'、R⁸'、R¹⁰、R¹¹And R¹²Each of which is independently selected from the group consisting of methyl, 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, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

A preferred embodiment of formula (I) is where M is Zr or Hf, Q is nitrogen, A ¹And A¹'both are carbon, E and E' are both oxygenAnd R is¹And R¹' all are C₄-C₂₀A cyclic tertiary alkyl group.

A preferred embodiment of formula (I) is where M is Zr or Hf, Q is nitrogen, A¹And A¹'are both carbon, E and E' are both oxygen, and R¹And R¹' are all adamantan-1-yl or substituted adamantan-1-yl.

Preferred embodiments of formula (I) are M is Zr or Hf, Q is nitrogen, A¹And A¹'both are carbon, E and E' both are oxygen, and R¹And R¹' both are C₆-C₂₀And (4) an aryl group.

A preferred embodiment of formula (II) is where M is Zr or Hf, E and E' are both oxygen, and R is¹And R¹' all are C₄-C₂₀A cyclic tertiary alkyl group.

A preferred embodiment of formula (II) is where M is Zr or Hf, E and E' are both oxygen, and R is¹And R¹' are all adamantan-1-yl or substituted adamantan-1-yl.

A preferred embodiment of formula (II) is where M is Zr or Hf, E and E' are both oxygen, and R is¹、R¹'、R³And R³Each of' is an adamantan-1-yl or substituted adamantan-1-yl group.

A preferred embodiment of the formula (II) is where M is Zr or Hf, E and E' are both oxygen, R¹And R¹' all are C₄-C₂₀Cyclic tertiary alkyl radical, and R⁷And R⁷' all are C₁-C₂₀An alkyl group.

Catalyst compounds particularly suitable for use in the present invention include one or more of the following: dimethylzirconium [2', 2' - (pyridine-2, 6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-phenate) ], dimethylhafnium [2', 2' - (pyridine-2, 6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-phenate) ], dimethylzirconium [6,6' - (pyridine-2, 6-diyl bis (benzo [ b ] thiophene-3, 2-diyl)) bis (2-adamantan-1-yl) -4-methylphenphenate) ], dimethylhafnium [6,6' - (pyridin-2, 6-diyl) bis (benzo [ b ] thiophen-3, 2-diyl)) bis (2-adamantan-1-yl) -4-methylphenoxide) ], dimethylzirconium [2', 2' "- (pyridin-2, 6-diyl) bis (3- ((3R,5R,7R) -adamantan-1-yl) -5-methyl- [1,1' -biphenyl ] -2-phenoxide) ], dimethylhafnium [2',2 '" - (pyridin-2, 6-diyl) bis (3- ((3R,5R,7R) -adamantan-1-yl) -5-methyl- [1,1' -biphenyl ] -2-phenoxide) ], dimethylzirconium [2', 2' - (pyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl ] -2-phenoxide) ], dimethylhafnium [2', 2' - (pyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl ] -2-phenoxide) ].

Catalyst compounds particularly useful in the present invention include those represented by one or more of the following formulae:

in some embodiments, two or more different catalyst compounds are present in the catalyst system used herein. In some embodiments, two or more different catalyst compounds are present in a reaction zone in which the process (es) described herein are carried out. When two transition metal compound-based catalysts are used in one reactor as a mixed catalyst system, the two transition metal compounds are preferably selected such that the two are compatible. Simple screening methods known to the person skilled in the art, for example by¹H or¹³C NMR can be used to determine which transition metal compounds are compatible. Preferably, the same activator is used for the transition metal compound, however, two different activators, such as a non-coordinating anion activator and an alumoxane, can be used in combination. If one or more of the transition metal compounds contains a group X which is not a hydride, hydrocarbyl or substituted hydrocarbyl group, the aluminoxy group may be allowedThe alkane is contacted with the transition metal compound prior to addition of the non-coordinating anion activator.

The two transition metal compounds (procatalysts) can be used in any ratio. (A) The preferred molar ratio of transition metal compound to (B) transition metal compound is in the range of 1:1000-1000:1, or 1:100-500:1, or 1:10-200:1, or 1:1-100:1, or 1:1-75:1, or 5:1-50:1 (A: B). The particular ratio selected will depend on the precise procatalyst selected, the method of activation, and the desired end product. In a particular embodiment, when two procatalysts are used, where both are activated with the same activator, useful mole% are 10-99.9% A and 0.1-90% B, or 25-99% A and 0.5-50% B, or 50-99% A and 1-25% B, or 75-99% A and 1-10% B, based on the molecular weight of the procatalyst.

Process for preparing catalyst compounds

Ligand synthesis

Bis (phenolic) ligands can be prepared using the general method shown in scheme 1. Formation of bis (phenolic) ligands by coupling of compound a with compound B (method 1) can be accomplished by known Pd-and Ni-catalyzed couplings, such as Negishi, Suzuki or Kumada couplings. Formation of bis (phenolic) ligands by coupling of compound C with compound D (method 2) can be accomplished by known Pd-and Ni-catalyzed couplings, such as Negishi, Suzuki or Kumada couplings. Compound D can be prepared from compound E as follows: reacting compound E with an organolithium reagent or magnesium metal, optionally followed by a main group metal halide (e.g., ZnCl) ₂) Or boron-based agents (e.g. B (O)ⁱPr)₃、ⁱPrOB (pin)) reaction. Compound E can be prepared in a non-catalytic reaction by reacting an aryl lithium or aryl Grignard reagent (compound F) with a dihalogenated aromatic hydrocarbon (compound G) such as 1-bromo-2-chlorobenzene. Compound E can also be prepared in a Pd-or Ni-catalyzed reaction by reacting an arylzinc or aryl-boron reagent (compound F) with a dihaloaromatic hydrocarbon (compound G).

Scheme 1

(method 1)

(method 2)

Wherein M' is a group 1, 2, 12 or 13 element or a substituted element, e.g. Li, MgCl, MgBr, ZnCl, B (OH)₂B (pinacol), P is a protecting group such as methoxymethyl (MOM), Tetrahydropyranyl (THP), t-butyl, allyl, ethoxymethyl, trialkylsilyl, t-butyldimethylsilyl or benzyl, R is C₁-C₄₀Alkyl, substituted alkyl, aryl, tertiary alkyl, cyclic tertiary alkyl, adamantyl or substituted adamantyl, and each X 'and X' is a halogen, such as Cl, Br, F or I.

It is preferred that the bis (phenol) ligand and the intermediate for preparing the bis (phenol) ligand are prepared and purified without using column chromatography. This can be achieved by a variety of methods including distillation, precipitation and washing, formation of insoluble salts (e.g. by reaction of pyridine derivatives with organic acids) and liquid-liquid extraction. Preferred methods include those described in Practical Process Research and Development-A Guide for Organic Chemists (ISBN:1493300125X) of New C.

Synthesis of carbene bis (phenol) ligands

A general synthetic method for preparing carbene bis (phenol) ligands is shown in scheme 2. The substituted phenol may be ortho-brominated and then protected with a known phenol protecting group such as MOM, THP, tert-butyldimethylsilyl (TBDMS), benzyl (Bn), and the like. The bromide is then converted to the boronic ester (compound I) or boronic acid, which can be used for Suzuki coupling with bromoaniline. Biphenylaniline (compound J) can be bridged by reaction with dibromoethane or by condensation with oxalaldehyde, and then deprotected (compound K). Reaction with triethyl orthoformate forms an iminium salt which is deprotonated to a carbene.

Scheme 2

To a substituted phenol (compound H) dissolved in dichloromethane was added 1 equivalent of N-bromosuccinimide and 0.1 equivalent of diisopropylamine. After stirring at ambient temperature until completion, the reaction was quenched with 10% HCl solution. The organic portion was washed with brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to afford bromophenol, typically as a solid. Substituted bromophenol, methoxymethyl chloride and potassium carbonate were dissolved in anhydrous acetone and stirred at ambient temperature until the reaction was complete. The solution was filtered and the filtrate was concentrated to give the protected phenol (compound I). Alternatively, the substituted bromophenol and one equivalent of dihydropyran are dissolved in dichloromethane and cooled to 0 ℃. Catalytic amounts of p-toluenesulfonic acid were added and the reaction was stirred for 10 minutes and then quenched with trimethylamine. The mixture was washed with water and brine, then dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give tetrahydropyran protected phenol.

Aryl bromide (compound I) was dissolved in THF and cooled to-78 ℃. N-butyllithium was added slowly followed by the addition of trimethoxyborate. The reaction was stirred at ambient temperature until completion. The solvent was removed and the solid borate was washed with pentane. Boronic acids can be prepared from boronic esters by treatment with HCl. The borate or boronic acid was dissolved in toluene with an equivalent amount of o-bromoaniline and a catalytic amount of tetrakis (triphenylphosphine) palladium. Aqueous sodium carbonate solution was added and the reaction was heated to reflux overnight. After cooling, the layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic portions were washed with brine and dried (MgSO)₄) Filtered and concentrated under reduced pressure. The coupled product (compound J) is usually purified using column chromatography.

Aniline (compound J) and dibromoethane (0.5 eq) were dissolved in acetonitrile and heated at 60 ℃ overnight. The reaction was filtered and concentrated to give the ethylene-bridged diphenylamine. Deprotection of the protected phenol by reaction with HCl affords the bridged bisamino (biphenyl) alcohol (compound K).

The diamine (compound K) was dissolved in triethyl orthoformate. Ammonium chloride was added and the reaction was heated to reflux overnight. A precipitate formed, which was collected by filtration and washed with ether to give the imine salt. The iminium chloride is suspended in THF and treated with lithium or sodium hexamethyldisilylamides. After completion, the reaction was filtered and the filtrate was concentrated to obtain the carbene ligand.

Preparation of bis (phenolate) complexes

Transition metal or lanthanide metal bis (phenolate) complexes are used in the present invention as catalyst components for olefin polymerization. The terms "catalyst" and "catalyst complex" are used interchangeably. The preparation of transition metal or lanthanide metal bis (phenolate) complexes may be accomplished by reaction of a bis (phenol) ligand with a metal reactant containing an anionic basic leaving group. Typical anionic basic leaving groups include dialkylamino, benzyl, phenyl, hydrogen, and methyl. In this reaction, the basic leaving group functions to deprotonate the bis (phenolic) ligand. Suitable metal reactants for this type of reaction include, but are not limited to, HfBn₄(Bn＝CH₂Ph)、ZrBn₄、TiBn₄、ZrBn₂Cl₂(OEt₂)、HfBn₂Cl₂(OEt₂)₂、Zr(NMe₂)₂Cl₂(dimethoxyethane), Hf (NMe)₂)₂Cl₂(dimethoxyethane), Hf (NMe)₂)₄、Zr(NMe₂)₄And Hf (NEt)₂)₄. Suitable metal reactants also include ZrMe₄、HfMe₄And other group 4 alkylates that may be formed in situ and used without isolation.

A second method of preparing transition metal or lanthanide bis (phenolate) complexes is to react the bis (phenol) ligand with an alkali or alkaline earth metal base (e.g., Na, BuLi, Cu, Mn, and S, or a,ⁱPrMgBr) to produce a deprotonated ligand, followed by reaction with a metal halide (e.g., HfCl)₄、ZrCl₄) To form a bis (phenolate) complex. Containing metal halide, alkoxide or amino leaving groups The bis (phenolate) metal complex of radicals may be alkylated by reaction with organolithium, grignard reagent and organoaluminum reactant. In the alkylation reaction, the alkyl group is transferred to the bis (phenolate) metal center and the leaving group is removed. Typical reactants for alkylation reactions include, but are not limited to, MeLi, MeMgBr, AlMe₃、Al(ⁱBu)₃、AlOct₃And PhCH₂MgCl. Typically 2 to 20 molar equivalents of the alkylating reagent are added to the bis (phenolate) complex. The alkylation is generally carried out in an ether or hydrocarbon solvent or solvent mixture at a temperature typically from-80 ℃ to 120 ℃.

Activating agent

The terms "cocatalyst" and "activator" are used interchangeably herein.

The catalyst systems described herein generally comprise a catalyst complex, such as a transition metal or lanthanide bis (phenoxide) complex as described above, and an activator, such as an alumoxane or a non-coordinating anion. These catalyst systems may be formed by combining the catalyst components described herein with activators in any manner known from the literature. The catalyst system may also be added to or generated from solution polymerization or bulk polymerization (in monomer). The catalyst system of the present disclosure may have one or more activators and one, two or more catalyst components. An activator is defined as any compound that can activate any of the above catalyst compounds by converting a neutral metal compound to a catalytically active metal compound cation. Non-limiting activators include, for example, alumoxanes, aluminum alkyls, ionizing activators (which may be neutral or ionic), and cocatalysts of conventional type. Preferred activators generally include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract reactive metal ligands, cationize the metal compound and provide a charge-balanced non-coordinating or weakly coordinating anion, such as a non-coordinating anion.

Alumoxane activators

Alumoxane activators are used as activators in the catalyst systems described herein. The aluminoxane usually contains-Al(R¹) -oligomer compounds of O-subunits, wherein R is¹Is an alkyl group. Examples of the aluminoxane include Methylaluminoxane (MAO), Modified Methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, especially when the abstractable ligand is an alkyl, halo, alkoxy or amino group. Mixtures of different aluminoxanes and modified aluminoxanes may also be used. It may be preferable to use methylaluminoxane which is visually transparent. The cloudy or gel aluminoxane can be filtered to prepare a clear solution or the clear aluminoxane can be decanted from the cloudy solution. Useful aluminoxanes are Modified Methylaluminoxane (MMAO) co-catalyst type 3A (commercially available from Akzo Chemicals, inc. under the trade name modified methylaluminoxane type 3A) covered by U.S. patent No. US 5,041,584. Another useful aluminoxane is US 9,340,630; solid polymethylaluminoxanes described in US 8,404,880 and US 8,975,209.

When the activator is an alumoxane (modified or unmodified), the maximum amount of activator is typically up to 5,000 times the molar excess of Al/M relative to the catalyst compound (per metal catalytic site). The minimum activator to catalyst compound ratio is 1:1 molar ratio. Alternative preferred ranges include 1:1 to 500:1, alternatively 1:1 to 200:1, alternatively 1:1 to 100:1, alternatively 1:1 to 50: 1.

In an alternative embodiment, little or no aluminoxane is used in the polymerization process described herein. Preferably, the aluminoxane is present in 0 mol% or the aluminoxane is present in a molar ratio of aluminum to transition metal of the catalyst compound of less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1: 1.

Ionic/non-coordinating anion activators

The term "non-coordinating anion" (NCA) refers to an anion that does not coordinate to the cation or that coordinates only weakly to the cation, thereby remaining sufficiently labile to be displaced by a neutral lewis base. In addition, the anion does not transfer an anionic substituent or moiety to the cation, causing it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions that can be used in accordance with the present invention are those that are compatible, stabilizing the transition metal cation at +1 in the sense of balancing its ionic charge, yet remain sufficiently labile to allow displacement during polymerization. The term NCA is also defined to include multi-component NCA-containing activators containing an acid-form cationic group and a non-coordinating anion, such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. The term NCA is also defined to include neutral lewis acids that can react with a catalyst to form an activated radical by extraction of an anionic group, such as tris (pentafluorophenyl) boron. Any metal or metalloid that can form a compatible, weakly coordinating complex can be used or contained in the non-coordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.

It is within the scope of the invention to use ionizing activators (neutral or ionic). It is also within the scope of the present invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.

In an embodiment of the invention, the activator is represented by formula (III):

(Z)_d ⁺(A^d-) (III)

wherein Z is (L-H) or a reducible Lewis acid, L is a neutral Lewis base; h is hydrogen; (L-H)⁺Is a bronsted acid; a. the^d-Is a non-coordinating anion having a charge d-; d is an integer of 1 to 3 (e.g. 1, 2 or 3), preferably Z is (Ar)₃C⁺) Wherein Ar is aryl or hetero atom, C₁To C₄₀Hydrocarbyl or substituted C₁To C₄₀Hydrocarbyl-substituted aryl. Anionic component A^d-Comprises a compound of the formula [ M^k+Q_n]^d-Wherein k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6 (preferably 1, 2, 3 or 4); n-k ═ d; m is an element selected from group 13 of the periodic table of the elements, preferably boron or aluminum, Q is independently hydrogen, bridged or unbridged dialkylamino, halo, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halocarbyl, said Q having up to 40 carbon atoms (optionally with the proviso that Q is not more than 1 time when Q is halo). PreferablyEach Q is a fluorinated hydrocarbon group having 1 to 40 (e.g., 1 to 20) carbon atoms, more preferably each Q is a fluorinated aryl group, such as a perfluorinated aryl group, most preferably each Q is a pentafluoroaryl group or a perfluoronaphthyl group. Is suitably A ^d-Also included are diboron compounds as disclosed in U.S. patent No. 5,447,895, which is incorporated herein by reference in its entirety.

When Z is an activating cation (L-H), it can be a Bronsted acid capable of donating a proton to a transition metal catalytic precursor to produce a transition metal cation comprising ammonium, oxygen

Sulfonium and mixtures thereof, such as methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, N-methyl-4-nonadecyl-N-octadecylaniline, N-methyl-4-octadecyl-N-octadecylaniline, diphenylamine, trimethylamine, triethylamine, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, ammonium dioctadecylmethylamine; phosphorus from triethylphosphine, triphenylphosphine and diphenylphosphine

From ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and diethyl ether

Oxygen of alkane

Sulfonium from sulfides such as diethyl sulfide, tetrahydrothiophene, and mixtures thereof.

In particularly useful embodiments of the invention, the activator is soluble in a non-aromatic hydrocarbon solvent, such as an aliphatic solvent.

In one or more embodiments, a 20 weight percent mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear, homogeneous solution at 25 ℃, preferably, a 30 weight percent mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear, homogeneous solution at 25 ℃.

In an embodiment of the invention, the activator described herein has a solubility in methylcyclohexane of greater than 10mM (or greater than 20mM, or greater than 50mM) at 25 ℃ (stirred for 2 hours).

In an embodiment of the invention, the activator described herein has a solubility in isohexane of greater than 1mM (or greater than 10mM, or greater than 20mM) at 25 deg.C (stirred for 2 hours).

In an embodiment of the invention, the activator described herein has a solubility in methylcyclohexane of greater than 10mM (or greater than 20mM, or greater than 50mM) at 25 ℃ (2 hours of stirring) and a solubility in isohexane of greater than 1mM (or greater than 10mM, or greater than 20mM) at 25 ℃ (2 hours of stirring).

In a preferred embodiment, the activator is a non-aromatic hydrocarbon soluble activator compound.

Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (V):

wherein:

e is nitrogen or phosphorus;

d is 1, 2 or 3; k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6; n-k ═ d (preferably d is 1, 2 or 3; k is 3; n is 4, 5 or 6);

R^1′、R^2′and R^3′Independently a C1-C50 hydrocarbon group optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups,

Wherein R is^1′、R^2′And R^3′Together containing 15 or more carbon atoms;

mt is an element selected from group 13 of the periodic Table of the elements, such as B or Al;

each Q is independently hydrogen, a bridged or unbridged dialkylamino group, halo, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, or halo-substituted hydrocarbyl.

Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (VI):

[R^1′R^2′R^3′EH]⁺[BR^4′R^5′R^6′R^7′]^- (VI)

wherein: e is nitrogen or phosphorus; r^1′Is methyl; r^2′And R^3′Independently is C optionally substituted with one or more alkoxy, silyl, halogen atoms or halogen-containing groups₄-C₅₀A hydrocarbon group, wherein R^2′And R^3′Together containing 14 or more carbon atoms; b is boron; and R^4′、R^5′、R^6′And R^7′Independently a hydrogen radical, a bridged or unbridged dialkylamido group, a halogen radical, an alkoxy radical, an aryloxy radical, a hydrocarbyl radical, a substituted hydrocarbyl radical, a halohydrocarbyl radical (halocarbyl radical), a substituted halocarbyl radical or a halo-substituted hydrocarbyl radical.

Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (VII) or formula (VIII):

and

wherein:

n is nitrogen;

R^2′and R^3′Independently is C optionally substituted with one or more alkoxy, silyl, halogen atoms or halogen-containing groups ₆-C₄₀A hydrocarbon group, whereinR^2′And R^3′Together (if present) contain 14 or more carbon atoms;

R^8′、R^9′and R^10′Independently is C₄-C₃₀Hydrocarbyl or substituted C4-C30 hydrocarbyl;

b is boron;

R^4′、R^5′、R^6′and R^7′Independently a hydrogen radical, a bridged or unbridged dialkylamido radical, a halogen radical, an alkoxy radical, an aryloxy radical, a hydrocarbyl radical, a substituted hydrocarbyl radical, a halogenated hydrocarbyl radical, a substituted halogenated hydrocarbyl radical, or a halogen-substituted hydrocarbyl radical.

Optionally, in any of formulae (V), (VI), (VII) or (VIII) herein, R^4′、R^5′、R^6′And R^7′Is pentafluorophenyl.

Optionally, in any of formulae (V), (VI), (VII) or (VIII) herein, R^4′、R^5′、R^6′And R^7′Is a pentafluoronaphthyl group.

Optionally, in any embodiment of formula (VIII) herein, R^8′And R^10′Is a hydrogen atom, R^9′Is C optionally substituted by one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups₄-C₃₀A hydrocarbyl group.

Optionally, in any embodiment of formula (VIII) herein, R^9′Is C optionally substituted by one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups₈-C₂₂A hydrocarbyl group.

Optionally, in any embodiment of formulae (VII) or (VIII) herein, R^2′And R^3′Independently is C₁₂-C₂₂A hydrocarbyl group.

Optionally, R^1′、R^2′And R ^3′Together containing 15 or more carbon atoms (e.g. 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbons)An atom, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms).

Optionally, R^2′And R^3′Together, comprise 15 or more carbon atoms (e.g. 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms).

Optionally, R^8′、R^9′And R^10′Together 15 or more carbon atoms (e.g. 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms).

Optionally, when Q is fluorophenyl, then R^2′Is not C₁-C₄₀Linear alkyl (or R)^2′C not being optionally substituted₁-C₄₀Linear alkyl).

Optionally, R^4′、R^5′、R^6′And R^7′Each of which is aryl (e.g. phenyl or naphthyl), wherein R^4′、R^5′、R^6′And R^7′Is substituted with at least one fluorine atom, preferably, R^4′、R^5′、R^6′And R^7′Each of which is a perfluoroaryl group (e.g., perfluorophenyl or perfluoronaphthyl).

Optionally, each Q is aryl (e.g., phenyl or naphthyl), wherein at least one of Q is substituted with at least one fluorine atom, preferably, each Q is perfluoroaryl (e.g., perfluorophenyl or perfluoronaphthyl).

Optionally, R^1′Is methyl; r^2′Is C₆-C₅₀An aryl group; r^3′Independently is C₁-C₄₀Linear alkyl or C₅-C₅₀And (4) an aryl group.

Optionally, R^2′And R^3′Each of which is independently unsubstituted or substituted with halo, C₁-C₃₅Alkyl radical, C₅-C₁₅Aryl radical, C₆-C₃₅Aralkyl radical, C₆-C₃₅At least one of the alkaryl radicals, wherein R²And R³Together containing 20 or more carbon atoms.

Optionally, each Q is independently hydrogen, a bridged or unbridged dialkylamino group, halo, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, or halo-substituted hydrocarbyl, provided that when Q is fluorophenyl, then R is ^2′Is not C₁-C₄₀Linear alkyl, preferably R^2′C not being optionally substituted₁-C₄₀Linear alkyl (or when Q is substituted phenyl, then R^2′Is not C₁-C₄₀Linear alkyl, preferably R^2′C not being optionally substituted₁-C₄₀Linear alkyl). Optionally, when Q is fluorophenyl (or when Q is substituted phenyl), then R^2′Is a meta-and/or para-substituted phenyl group wherein the meta-and para-substituents are independently optionally substituted C₁To C₄₀Hydrocarbyl radicals (e.g. C)₆To C₄₀Aryl or linear alkyl, C₁₂To C₃₀Aryl or linear alkyl, or C₁₀To C₂₀Aryl or linear alkyl), optionally substituted alkoxy or optionally substituted silyl. Optionally, each Q is a fluorinated hydrocarbon group containing 1 to 30 carbon atoms, more preferably each Q is a fluorinated aryl group (e.g., phenyl or naphthyl), and most preferably each Q is a fluorinated aryl group (e.g., phenyl or naphthyl). Adapted [ Mt^k+Q_n]^d-Also included are diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is incorporated herein by reference in its entirety. Optionally, toOne less Q is not substituted phenyl. Optionally, all Q are not substituted phenyl. Optionally, at least one Q is not perfluorophenyl. Optionally, all Q are not perfluorophenyl.

In some embodiments of the invention, R^1′Not being methyl, R^2′Is not C₁₈Alkyl radical, R^3′Is not C₁₈Alkyl, or R^1′Not being methyl, R^2′Is not C₁₈Alkyl radical, R^3′Is not C₁₈Alkyl, and at least one Q is not substituted phenyl, optionally all Q are not substituted phenyl.

Useful cationic components in formulas (III) and (V) to (VIII) include those represented by the following formulas:

the anionic component of the activators described herein includes compounds represented by the formula [ Mt^k+Q_n]^-Those represented, wherein k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6 (preferably 1, 2, 3 or 4), (preferably k is 3; n is 4, 5 or 6, preferably n is 4 when M is B); mt is an element selected from group 13 of the periodic table of the elements, preferably boron or aluminum, and Q is independently hydrogen, bridged and unbridged dialkylamido, halo, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl and halo-substituted hydrocarbyl, the Q group having up to 20 carbon atoms, with the proviso that Q does not exceed 1 occurrence of halo. Preferably, each Q is a fluorinated hydrocarbon group, optionallyDesirably from 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a perfluorinated aryl group. Preferably, at least one Q is not substituted phenyl, such as perfluorophenyl, preferably all Q are not substituted phenyl, such as perfluorophenyl.

In one embodiment, the borate activator comprises tetrakis (heptafluoronaphthalen-2-yl) borate.

In one embodiment, the borate activator comprises tetrakis (pentafluorophenyl) borate.

The anions for the non-coordinating anion activators described herein also include those represented by the following formula 7:

wherein:

m is a group 13 atom, preferably B or Al, preferably B;

each R¹¹Independently a halo group, preferably a fluoro group;

each R¹²Independently of one another is halo, C₆-C₂₀Substituted aromatic hydrocarbon radicals or radicals of the formula-O-Si-R^aSiloxy of (a) wherein R is^aIs C₁-C₂₀Hydrocarbyl or hydrocarbylsilyl, preferably R¹²Is fluoro or perfluorinated phenyl;

each R¹³Is halo, C₆-C₂₀Substituted aromatic hydrocarbon radicals or radicals of the formula-O-Si-R^aSiloxy of (a) wherein R is^aIs C₁-C₂₀Hydrocarbyl or hydrocarbylsilyl, preferably R¹³Is fluoro or C6 perfluorinated aromatic hydrocarbon;

wherein R is¹²And R¹³May form one or more saturated or unsaturated, substituted or unsubstituted rings, preferably R¹²And R¹³A perfluorinated benzene ring is formed. Preferably, the anion has a molecular weight of more than 700g/mol, and preferably, at least three of the substituents on M atoms each have a volume of more than 180 cubic

Molecular volume of (c).

"molecular volume" is used herein as an approximation of the steric volume of the activator molecule in solution. Comparison of substituents having different molecular volumes allows substituents having smaller molecular volumes to be considered "less bulky" than substituents having larger molecular volumes. Conversely, a substituent having a larger molecular volume may be considered "bulkier" than a substituent having a smaller molecular volume.

Molecular Volumes can be calculated as reported in "A Simple" Back of the Environment "Method for Estimating the concentrations and Molecular Volumes of Liquids and solutions," Journal of Chemical Equipment, v.71(11), November 1994, pp.962-964. Molecular Volume (MV) (in unit of

) Calculated using the formula MV ═ 8.3V_sIn which V is_sIs the zoom volume. V_sIs the sum of the relative volumes of the constituent atoms, and is calculated from the formula of the substituent using the relative volumes of table a below. For condensed rings, V of each condensed ring_sThe reduction is 7.5%. The calculated total MV of the anions being the sum of the MVs per substituent, e.g. the MV of the perfluorophenyl group being

The calculated total MV of the tetrakis (perfluorophenyl) borate is

Four times or

TABLE A

Element(s)	Relative volume
		H	1
First short term, Li-F	2
		Second short term, Na-Cl	4
First long term, K-Br	5
		Second long-term, Rb-I	7.5
Third long-term, Cs-Bi	9

Exemplary anions useful herein and their respective scaled volumes and molecular volumes are shown in table B below. The dashed bonds indicate bonding with boron.

TABLE B

The activator may be, for example, [ M2HTH ]]⁺[NCA]^-Added to the polymerization in the form of an ion pair, wherein a bis (hydrogenated tallow) methylamine ("M2HTH") cation reacts with a basic leaving group on the transition metal complex to form the transition metal complex Cation and [ NCA ]]^-. Alternatively, the transition metal complex may be reacted with a neutral NCA precursor, such as B (C)₆F₅)₃Reaction, which extracts anionic groups from the complex to form an activated species. Useful activators include [ tetrakis (pentafluorophenyl) borate]Bis (hydrogenated tallow) methylammonium (i.e., [ M ]₂HTH]B(C₆F₅)₄) And [ tetrakis (pentafluorophenyl) borate]Dioctadecyl tolylammonium (i.e., [ DOdTH ]]B(C₆F₅)₄)。

Activator compounds particularly useful in the present invention include one or more of the following:

[ tetrakis (perfluorophenyl) borate ] N, N-bis (hydrogenated tallow) methylammonium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-4-nonadecyl-N-octadecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-4-hexadecyl-N-octadecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-4-tetradecyl-N-octadecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-4-dodecyl-N-octadecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-4-decyl-N-octadecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-4-octyl-N-octadecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-4-hexyl-N-octadecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-4-butyl-N-octadecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-4-octadecyl-N-decylphenylammonium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-4-nonadecyl-N-dodecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-4-nonadecyl-N-tetradecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-4-nonadecyl-N-hexadecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-ethyl-4-nonadecyl-N-octadecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-N, N-dioctadecylammonium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-N, N-dihexadecylammonium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-N, N-ditetraalkylammonium,

N-methyl-N, N-didodecylammonium tetrakis (perfluorophenyl) borate,

[ tetrakis (perfluorophenyl) borate ] N-methyl-N, N-didecylammonium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-N, N-dioctylammonium,

[ tetrakis (perfluorophenyl) borate ] N-ethyl-N, N-dioctadecylammonium,

[ Tetrakis (perfluorophenyl) boronic acid ] N, N-dioctadecyl tolylammonium,

n, N-dihexadecyl tolylammonium tetrakis (perfluorophenyl) borate,

[ tetrakis (perfluorophenyl) borate ] N, N-ditetradecylthylammonium,

n, N-didodecyl tolylammonium tetrakis (perfluorophenyl) borate,

[ tetrakis (perfluorophenyl) borate ] N-octadecyl-N-hexadecyl-tolylammonium,

[ tetrakis (perfluorophenyl) borate ] N-octadecyl-N-tetradecyl-tolylammonium,

[ tetrakis (perfluorophenyl) borate ] N-octadecyl-N-dodecyl-tolylammonium,

[ tetrakis (perfluorophenyl) borate ] N-octadecyl-N-decyl-tolylammonium,

[ tetrakis (perfluorophenyl) borate ] N-hexadecyl-N-tetradecyl-tolylammonium,

[ tetrakis (perfluorophenyl) borate ] N-hexadecyl-N-dodecyl-tolylammonium,

[ tetrakis (perfluorophenyl) borate ] N-hexadecyl-N-decyl-tolylammonium,

[ tetrakis (perfluorophenyl) borate ] N-tetradecyl-N-dodecyl-tolylammonium,

[ tetrakis (perfluorophenyl) borate ] N-tetradecyl-N-decyl-tolylammonium,

N-dodecyl-N-decyl-tolylammonium tetrakis (perfluorophenyl) borate,

[ tetrakis (perfluorophenyl) borate ] N-methyl-N-octadecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-N-hexadecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-N-tetradecylphenylammonium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-N-dodecylanilinium,

[ tetrakis (perfluorophenyl) borate ] N-methyl-N-decylphenylammonium, and

[ tetrakis (perfluorophenyl) borate ] N-methyl-N-octylanilinium.

Other useful activators and synthetic non-aromatic hydrocarbon soluble activators are described in USSN 16/394,166, filed on 25.4.2019, USSN 16/394,186, filed on 25.4.2019, and USSN 16/394,197, filed on 25.4.2019, which are incorporated herein by reference.

Likewise, particularly useful activators include dimethylanilinium tetrakis (pentafluorophenyl) borate and dimethylanilinium tetrakis (heptafluoro-2-naphthyl) borate. For a more detailed description of useful activators, see WO 2004/026921, page 72, paragraph to page 81, paragraph. A list of further particularly useful activators which can be used in the practice of the present invention can be found in page 72, paragraph to page 74, paragraph of WO 2004/046214.

For a description of useful activators, see US 8,658,556 and US 6,211,105.

Preferred activators for use herein also include N-methyl-4-nonadecyl-N-octadecylanilinium tetrakis (pentafluorophenyl) borate, N-methyl-4-nonadecyl-N-octadecylanilinium tetrakis (perfluoronaphthyl) borate, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N-dimethylanilinium tetrakis (perfluorophenyl) borate, N-dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate

Triphenylcarbon tetrakis (perfluorobiphenyl) borate

Triphenylcarbenium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

Triphenylcarbenium tetrakis (perfluorophenyl) borate

[Me₃NH⁺][B(C₆F₅)₄-](ii) a 1- (4- (tris (pentafluorophenyl) boronic acid) -2,3,5, 6-tetrafluorophenyl) pyrrolidine

And tetrakis (pentafluorophenyl) borate, 4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluoropyridine.

In a preferred embodiment, the activator comprises a triaryl carbon

(e.g. triphenylcarbeniumtetraphenylborate)

Triphenylcarbenium tetrakis (pentafluorophenyl) borate

Triphenylcarbenium tetrakis (2,3,4, 6-tetrafluorophenyl) borate

Triphenylcarbon tetrakis (perfluoronaphthyl) borate

Triphenylcarbon tetrakis (perfluorobiphenyl) borate

Triphenylcarbenium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

)。

In another embodiment, the activator comprises one or more of the following: trialkylammonium tetrakis (pentafluorophenyl) borate, N-dialkylanilinium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (perfluoronaphthyl) borate, N-dimethyl- (2,4, 6-trimethylphenylammonium tetrakis (pentafluorophenyl) borate, trialkylammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, N-dialkylanilinium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, trialkylammonium tetrakis (perfluoronaphthyl) borate, N-dialkylanilinium tetrakis (perfluoronaphthyl) borate, trialkylammonium tetrakis (perfluorobiphenyl) borate, N-dialkylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, trialkylammonium tetrakis (perfluorobiphenyl) borate, trialkylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, and mixtures thereof, N, N-dialkylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, N-dialkyl- (2,4, 6-trimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate, (where alkyl is methyl, ethyl, propyl, N-butyl, sec-butyl or tert-butyl).

Typical activator to catalyst ratios, for example all NCA activator to catalyst ratios are about 1:1 molar ratios. Alternative preferred ranges include from 0.1:1 to 100:1, alternatively from 0.5:1 to 200:1, alternatively from 1:1 to 500:1, alternatively from 1:1 to 1000: 1. A particularly useful range is from 0.5:1 to 10:1, preferably from 1:1 to 5: 1.

It is also within the scope of the present disclosure that the catalyst compound may be combined with an aluminoxane and NCA combination (see, e.g., U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,453,410; EP 0573120B 1; WO 1994/007928; and WO 1995/014044, the disclosures of which are incorporated herein by reference in their entirety), which discuss the use of aluminoxanes in combination with ionizing activators.

Optionally scavengers, co-activators, chain transfer agents

In addition to the activator compound, a scavenger or co-activator may be used. Scavengers are compounds that are typically added to promote polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. Co-activators (not scavengers) may also be used in combination with the activator to form an active catalyst. In some embodiments, the co-activator may be premixed with the transition metal compound to form an alkylated transition metal compound.

The co-activator may include alumoxanes such as methylalumoxane, modified alumoxanes such as modified methylalumoxane and alkyl aluminums such as trimethylaluminum, tri-isobutylaluminum, triethylaluminum and tri-isopropylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum or tri-n-dodecylaluminum. When the current catalyst is not a dihydrocarbyl or dihydride complex, the co-activator is typically used in combination with a lewis acid activator and an ionic activator. Sometimes the co-activator also acts as a scavenger to passivate impurities in the feed or the reactor.

Aluminum alkyls or organoaluminum compounds that can be used as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and dialkylzinc, diethylzinc.

Chain transfer agents may be used in the compositions and/or methods described herein. Useful chain transfer agents are typically hydrogen, alkylaluminoxanes, compounds of the formula AlR₃、ZnR₂A compound of (wherein each R is independently C)₁-C₈Aliphatic groups, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof) or combinations thereof, for example diethyl zinc, trimethylaluminum, triisobutylaluminum, trioctylaluminum or combinations thereof.

Polymerization process

For the polymerization process described herein, the term "continuous" refers to a system that operates without interruption or stoppage. For example, a continuous process for producing a polymer would be one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

Solution polymerization refers to a polymerization process in which the polymer is dissolved in a liquid phase polymerization medium, such as an inert solvent or monomer or blends thereof. Solution polymerization is generally homogeneous. Homogeneous polymerization is polymerization in which the polymer product is dissolved in the polymerization medium. Such systems are preferably not turbid as described in j.vladimir oliverira et al (2000) ind. chem. res., v.29, page 4627.

Bulk polymerization refers to a polymerization process in which the monomer and/or comonomer being polymerized is used as a solvent or diluent with little use of an inert solvent as a solvent or diluent. A small portion of an inert solvent may be used as a carrier for the catalyst and scavenger. The bulk polymerization system contains less than 25 wt% of inert solvent or diluent, preferably less than 10 wt%, preferably less than 1 wt%, preferably 0 wt%.

In embodiments herein, the present invention relates to a polymerization process wherein a monomer (e.g., propylene) and optional comonomers are contacted with a catalyst system comprising an activator and at least one catalyst compound described above. The catalyst compound and activator can be combined in any order and are typically combined prior to contacting with the monomer.

Monomers useful herein include substituted or unsubstituted C₂-C₄₀Alpha-olefins, preferably C₂-C₂₀Alpha-olefins, preferably C₂-C₁₂Alpha-olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In a preferred embodiment of the invention, the monomers comprise propylene and optionally comonomers comprising one or more of ethylene or C₄-C₄₀Olefins, preferably C₄-C₂₀Olefins, or preferably C₆-C₁₂An olefin. C₄-C₄₀The olefin monomers may be linear, branched or cyclic. C₄-C₄₀The cyclic olefin may be strained (strained) or unstrained (unstrained), monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups. In another preferred embodiment, the monomers comprise ethylene and optionally comonomers comprising one or more C₃-C₄₀Olefins, preferably C₄-C₂₀Olefins, or preferably C₆-C₁₂An olefin. The C is₃-C₄₀The olefin monomers may be linear, branched or cyclicIn (1). The C is₃-C₄₀The cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.

Exemplary C₂-C₄₀Olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, cyclopentene, cycloheptene, cyclooctene, cyclododecene, substituted derivatives thereof and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 5-methylcyclopentene, cyclopentene, norbornene, 5-ethylidene-2-norbornene and corresponding homologs and derivatives thereof.

In a preferred embodiment, one or more dienes are present in the polymer made herein in an amount of up to 10 weight percent, preferably from 0.00001 to 1.0 weight percent, preferably from 0.002 to 0.5 weight percent, even more preferably from 0.003 to 0.2 weight percent, based on the total weight of the composition. In some embodiments, 500ppm or less of diene, preferably 400ppm or less, preferably 300ppm or less, is added to the polymerization. In other embodiments, at least 50ppm of diene, or 100ppm or more, or 150ppm or more is added to the polymerization.

Preferred diene monomers useful in the present invention include any hydrocarbon structure having at least two unsaturated bonds, preferably C₅-C₃₀Wherein at least two of said unsaturated bonds are readily incorporated into the polymer by a stereospecific or non-stereospecific catalyst. It is further preferred that the diene monomer is selected from non-conjugated diene monomers. More preferably, the diolefin monomers are linear divinyl monomers, most preferably those containing from 5 to 30 carbon atoms. Examples of preferred dienes include pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, eicosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene Twenty-six-carbon diene, twenty-seven-carbon diene, twenty-eight-carbon diene, twenty-nine-carbon diene, thirty-carbon diene, particularly preferred dienes include 1, 6-heptadiene, 1, 7-octadiene, 1, 8-nonadiene, 1, 9-decadiene, 1, 10-undecadiene, 1, 11-dodecadiene, 1, 12-tridecadiene, 1, 13-tetradecadiene, divinylbenzene and low molecular weight polybutadiene (Mw less than 1000 g/mol). Preferred cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, and dicyclopentadiene.

The polymerization process of the present invention may be carried out in any manner known in the art. Any suspension, homogeneous, bulk, solution, slurry or gas phase polymerization process known in the art may be used. These processes can be tested in batch, semi-batch or continuous mode. Homogeneous polymerization processes and slurry processes are preferred. (A homogeneous polymerization process is preferably one in which at least 90% by weight of the product is soluble in the reaction medium). Bulk homogeneous processes are particularly preferred. (the bulk process is preferably one in which the monomer concentration in all feeds to the reactor is 70% or more by volume.) alternatively, a solvent or diluent is not present in or added to the reaction medium (except for small amounts which serve as a support for the catalyst system or other additives, or amounts which are typically used in conjunction with the monomer, such as propane in propylene). In another embodiment, the process is a slurry process. The term "slurry polymerization process" as used herein refers to a polymerization process wherein a supported catalyst is used and monomers are polymerized on the supported catalyst particles. At least 95 wt% of the polymer product derived from the supported catalyst is particulate as solid particles (insoluble in the diluent).

Suitable diluents/solvents for the polymerization include non-coordinating inert liquids. Examples include linear and branched hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof such as those commercially available (Isopar)^TMA fluid); perhalogenated hydrocarbons, e.g. perfluorinated C_4-10Examples of alkanes, chlorobenzenes and aromatic and alkyl-substituted aromatic compoundsSuch as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins that may serve as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. In a preferred embodiment, aliphatic hydrocarbon solvents are used as solvents, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof. In another embodiment, the solvent is a non-aromatic solvent, preferably the aromatic compound is present in the solvent at less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0 wt%, based on the weight of the solvent.

In a preferred embodiment, the feed concentration of the monomers and comonomers used for polymerization is 60 vol% solvent or less, preferably 40 vol% or less, preferably 20 vol% or less, based on the total volume of the feed streams. Preferably, the polymerization is tested in bulk.

The preferred polymerizations can be tested at any temperature and/or pressure suitable to obtain the desired ethylene polymer. Typical temperatures and/or pressures include temperatures of from about 0 ℃ to about 300 ℃, preferably from about 20 ℃ to about 200 ℃, preferably from about 35 ℃ to about 150 ℃, preferably from about 40 ℃ to about 120 ℃, preferably from about 45 ℃ to about 80 ℃; and at a pressure of from about 0.35MPa to about 10MPa, preferably from about 0.45MPa to about 6MPa, or preferably from about 0.5MPa to about 4 MPa.

In a typical polymerization, the run time for the reaction is up to 300 minutes, preferably about 5 to 250 minutes, or preferably about 10 to 120 minutes.

In some embodiments, hydrogen is present in the polymerization reactor at a partial pressure of from 0.001 to 50psig (0.007 to 345kPa), preferably from 0.01 to 25psig (0.07 to 172kPa), more preferably from 0.1 to 10psig (0.7 to 70 kPa).

In an alternative embodiment, the catalyst activity is at least 10,000 g/mmol/hr, preferably 100,000 g/mmol/hr or more, preferably 500,000g/mmol/hr or more, preferably 1,000,000g/mmol/hr or more, preferably 2,000,000g/mmol/hr or more, preferably 5,000,000g/mmol/hr or more. In an alternative embodiment, the conversion of olefin monomer is at least 10%, preferably 20% or more, preferably 30% or more, preferably 50% or more, preferably 80% or more, based on the polymer production and weight of monomer entering the reaction zone.

In a preferred embodiment, little or no aluminoxane is used in the process for preparing the polymers. Preferably, the aluminoxane is present in zero mole%, or the aluminoxane is present in a molar ratio of aluminum to transition metal of less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1: 1.

In a preferred embodiment, little or no scavenger is used in the process for preparing the ethylene polymer. Preferably, the scavenger (e.g., trialkylaluminum) is present at zero mol%, or the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, preferably less than 50:1, preferably less than 15:1, preferably less than 10: 1.

In a preferred embodiment, the polymerization: 1) at a temperature of 0-300 ℃ (preferably 25-150 ℃, preferably 40-120 ℃, preferably 45-80 ℃, preferably 60-160 ℃); 2) at a pressure of from atmospheric pressure to 10MPa (preferably from 0.35 to 10MPa, preferably from 0.45 to 6MPa, preferably from 0.5 to 4 MPa); 3) in an aliphatic hydrocarbon solvent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; preferably wherein the aromatic compound is present in the solvent in less than 1 wt.%, preferably less than 0.5 wt.%, preferably in 0 wt.%, based on the weight of the solvent); 4) wherein the catalyst system for the polymerization comprises less than 0.5 mol%, preferably 0 mol% of aluminoxane or the aluminoxane is present in a molar ratio of aluminum to transition metal of less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1: 1; 5) the polymerization is preferably carried out in one reaction zone; 6) a catalyst activity of at least 10,000g/mmol/hr (preferably at least 100,000g/mmol/hr, preferably at least 200,000g/mmol/hr, preferably at least 500,000g/mmol/hr, preferably at least 1,000,000g/mmol/hr, preferably at least 2,000,000g/mmol/hr, preferably at least 5,000,000 g/mmol/hr); 7) optionally, a scavenger (e.g., a trialkylaluminum compound) is absent (e.g., present at zero mol%, or the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, preferably less than 50:1, preferably less than 15:1, preferably less than 10: 1); and 8) optionally, hydrogen is present in the polymerization reactor at a partial pressure of from 0.001 to 50psig (0.007 to 345kPa), preferably from 0.01 to 25psig (0.07 to 172kPa), more preferably from 0.1 to 10psig (0.7 to 70 kPa). In a preferred embodiment, the catalyst system used in the polymerization comprises at most one catalyst compound. A "reaction zone" also referred to as a "polymerization zone" is a vessel in which polymerization is carried out, such as a batch reactor. When multiple reactors are used in a series or parallel configuration, each reactor is considered a separate polymerization zone. For multi-stage polymerization in both batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. In a preferred embodiment, the polymerization is carried out in one reaction zone. The room temperature was 23 ℃ unless otherwise specified.

Other additives may also be used in the polymerization, as desired, such as one or more scavengers, hydrogen, aluminum alkyls, silanes, or chain transfer agents (e.g., alkylaluminoxanes, of the formula AlR₃Or ZnR₂A compound of (wherein each R is independently C)₁-C₈Aliphatic groups, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof) or combinations thereof, such as diethyl zinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum or combinations thereof).

Polyolefin products

The invention also relates to compositions of matter prepared by the methods described herein. The process described herein can be used to prepare polymers of olefins or mixtures of olefins. Polymers that may be prepared include polyethylene, polypropylene, C₄-C₂₀Homopolymers of olefins, C₄-C₂₀Copolymers of olefins, ethylene and C₃-C₂₀Copolymers of olefins, propylene and C₄-C₂₀Copolymers of olefins, C₄-C₂₀Terpolymers of olefins, ethylene and propylene with C₄-C₂₀Terpolymers of olefins and terpolymers of ethylene and propylene with 5-ethylidene-2-norbornene.

In a preferred embodiment, the process described herein produces propylene homopolymers or propylene copolymers, for example propylene-ethylene and/or propylene-alpha-olefins (preferably C) having Mw/Mn from 1 to 10 (preferably from 2 to 5, preferably from 2 to 4, preferably from 2 to 3) ₄-C₂₀) Copolymers (e.g., propylene-hexene copolymers or propylene-octene copolymers).

In a preferred embodiment, the polymers prepared herein are preferably of 0 to 25 mole% (alternatively 0.5 to 20 mole%, alternatively 1 to 15 mole%, preferably 3 to 10 mole%) of one or more C₃-C₂₀Olefin comonomer (preferably C)₃-C₁₂Ethylene copolymers of alpha-olefins, preferably propylene, butene, hexene, octene, decene, dodecene, preferably propylene, butene, hexene, octene), or preferably having from 0 to 25 mole% (or from 0.5 to 20 mole%, or from 1 to 15 mole%, preferably from 3 to 10 mole%) of one or more C₂Or C₄-C₂₀Olefin comonomer (preferably ethylene or C)₄-C₁₂Propylene copolymers of alpha-olefins, preferably ethylene, butene, hexene, octene, decene, dodecene, preferably ethylene, butene, hexene, octene).

In a preferred embodiment, the monomer is ethylene and the comonomer is hexene, preferably 1 to 15 mole% hexene, alternatively 1 to 10 mole%.

Generally, the polymers prepared herein have a Mw of 5,000-1,000,000g/mol (preferably 25,000-750,000g/mol, preferably 50,000-500,000g/mol) and/or a Mw/Mn of greater than 1 to 40 (or 1.2-20, or 1.3-10, or 1.4-5, 1.5-4, or 1.5-3).

In a preferred embodiment, the polymers produced herein have a monomodal or multimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC). By "unimodal" is meant that the GPC trace has one peak or inflection point. By "multimodal" is meant that the GPC trace has at least two peaks or inflection points. An inflection point is a point where the second derivative of the curve changes sign (e.g., from negative to positive, or vice versa).

Blends

In another embodiment, the polymer (preferably polyethylene or polypropylene) produced herein is combined with one or more additional polymers prior to forming a film, molded part, or other article. Other useful polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymers of propylene and ethylene and/or butene and/or hexene, polybutene, ethylene-vinyl acetate, LDPE, LLDPE, HDPE, ethylene-vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethyl methacrylate or any other polymer polymerizable by the high pressure free radical process, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resins, ethylene-propylene rubbers (EPR), vulcanized EPR, EPDM, block copolymers, styrenic block copolymers, polyamino, polycarbonate, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetals, polyvinylidene fluoride, polyethylene glycol and/or polyisobutylene.

In a preferred embodiment, the polymer (preferably polyethylene or polypropylene) is present in the above-described blend in an amount of from 10 to 99 weight percent, preferably from 20 to 95 weight percent, even more preferably at least 30 to 90 weight percent, even more preferably at least 40 to 90 weight percent, even more preferably at least 50 to 90 weight percent, even more preferably at least 60 to 90 weight percent, even more preferably at least 70 to 90 weight percent, based on the weight of the polymer in the blend.

The above blends can be prepared as follows: the polymers of the present invention are mixed with one or more polymers (as described above), reactors are connected together in series to produce a reactor blend or more than one catalyst is used in the same reactor to produce a multiple polymer mass. The polymers may be mixed together prior to being fed into the extruder or may be mixed in the extruder.

The blend may be formed using conventional equipment and methods, such as dry blending the components and then melt mixing in a mixer, or mixing the componentsMixing together directly in a mixer such as a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin screw extruder, which may include compounding extruders and side arm extruders used directly downstream of the polymerization process, which may include blending powders or pellets of the resin at the hopper of a film extruder. Further, additives may be included in the blend, in one or more components of the blend, and/or in a product formed from the blend, such as a film, as desired. Such additives are well known in the art and may include, for example: a filler; antioxidants (e.g., hindered phenols such as IRGANOX, available from Ciba-Geigy ^TM1010 or IRGANOX^TM1076) (ii) a Phosphites (e.g., IRGAFOS available from Ciba-Geigy^TM168) (ii) a An anti-stiction additive; tackifiers such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates and hydrogenated rosin; a UV stabilizer; a heat stabilizer; an anti-blocking agent; an anti-sticking agent; an antistatic agent; a pigment; a colorant; a dye; a wax; silicon oxide; a filler; talc, and the like.

Any of the above polymers and compositions, in combination with optional additives (see, e.g., U.S. patent application publication No. 2016/0060430, paragraph), can be used in a variety of end-use applications. Such end uses may be prepared by methods known in the art. End uses include polymeric products and products having a particular end use. Exemplary end uses can include, but are not limited to, films, film-based products, diaper backsheets, industrial filter cloths, wire and cable coating compositions, articles formed by molding techniques such as injection or blow molding, extrusion coating, foaming, casting, and combinations thereof. End uses also include products made from films, such as bags, packaging, and personal care films, packets, medical products, such as medical films and Intravenous (IV) bags.

Film

In particular, any of the above-described polymers, such as the above-described polypropylenes or blends thereof, can be used in a variety of end-use applications. Such applications include, for example, single or multilayer blown, extruded and/or shrink films. These films can be formed by a number of well-known extrusion or coextrusion techniques, such as the blown bubble film processing technique, in which the composition can be extruded in a molten state through an annular die, then expanded to form a uniaxially or biaxially oriented melt, then cooled to form a tube, blown film, and then can be axially cut and unfolded to form a flat film. The film may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents. One or more of the film layers may be oriented in the transverse and/or machine direction to the same or different extents. Uniaxial orientation can be performed using typical cold or hot stretching methods. Biaxial orientation may be performed using a tenter frame apparatus or a double bubble process and may be performed before or after assembly of the various layers. For example, a polyethylene layer may be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene may be coextruded together into a film and then oriented. Likewise, oriented polypropylene may be laminated to oriented polyethylene or oriented polyethylene may be coated onto polypropylene, and then optionally the assembly may be even further oriented. Typically, the film is oriented in the Machine Direction (MD) in a proportion of at most 15, preferably 5 to 7, and in the Transverse Direction (TD) in a proportion of at most 15, preferably 7 to 9. However, in another embodiment, the film is oriented to the same extent in both the MD and TD directions.

The thickness of the film may vary depending on the intended application; however, films of thickness from 1 μm to 50 μm are generally suitable. Films intended for packaging are typically 10-50 μm thick. The thickness of the sealing layer is typically 0.2-50 μm. The sealant layer may be present on both the inner and outer surfaces of the film or the sealant layer may be present only on the inner or outer surface.

In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave. In a preferred embodiment, one or both of the surface layers are modified by corona treatment.

In another embodiment, the present invention relates to:

1. a catalyst compound represented by the following formula (I):

wherein:

m is a group 3, 4, 5 or 6 transition metal or a lanthanide;

q is a group 14, 15 or 16 atom that forms a coordinate bond with metal M;

A¹QA¹' is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, which bridges A via a 3-atom bridge²Is connected to A²', wherein Q is the central atom of the 3-atom bridge, A¹And A ¹' independently is C, N or C (R)²²) Wherein R is²²Selected from hydrogen, C₁-C₂₀Hydrocarbyl radical, C₁-C₂₀A substituted hydrocarbyl group;

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 more than 4;

R¹、R²、R³、R⁴、R¹'、R²'、R³' and R⁴Each of' is independently hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group,

and R is¹And R²、R²And R³、R³And R⁴、R¹' and R²'、R²' and R³'、R³' and R⁴One or more pairs of' may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic or unsubstituted heterocyclic rings, each having 5, 6, 7 or 8 ring atoms, and wherein substituents on the rings may join to form additional rings;

any two L groups may be joined together to form a bidentate lewis base;

the X group may be joined to the L group to form a monoanionic bidentate group;

any two X groups may be joined together to form a dianionic ligand group.

2. A catalyst compound of formula 1, wherein the catalyst compound is represented by formula (II):

Wherein:

m is a group 3, 4, 5 or 6 transition metal or a lanthanide;

each L is independently a lewis base;

each X is independently an anionic ligand;

n is 1, 2 or 3;

m is 0, 1 or 2;

n + m is not more than 4;

R¹、R²、R³、R⁴、R¹'、R²'、R³' and R⁴' each of which is independentGround is hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R¹And R²、R²And R³、R³And R⁴、R¹' and R²'、R²' and R³'、R³' and R⁴One or more pairs of' may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic or unsubstituted heterocyclic rings, each having 5, 6, 7 or 8 ring atoms, and wherein substituents on the rings may join to form additional rings;

any two L groups may be joined together to form a bidentate lewis base;

the X group may be joined to the L group to form a monoanionic bidentate group;

any two X groups may be joined together to form a dianionic ligand group;

R⁵、R⁶、R⁷、R⁸、R⁵'、R⁶'、R⁷'、R⁸'、R¹⁰、R¹¹and R¹²Each of which is independently hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R ⁵And R⁶、R⁶And R⁷、R⁷And R⁸、R⁵' and R⁶'、R⁶' and R⁷'、R⁷' and R⁸'、R¹⁰And R¹¹Or R¹¹And R¹²One or more pairs of (a) 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, and wherein substituents on the rings may join to form additional rings.

3. The catalyst compound of paragraph 1 or 2 wherein M is Hf, Zr or Ti.

4. The catalyst compound of paragraph 1, 2 or 3, wherein E and E' are each O.

5. Catalyst of stage 1, 2, 3 or 4A compound of formula (I) wherein R¹And R¹' independently is C₄-C₄₀A tertiary hydrocarbon group.

6. The catalyst compound of paragraph 1, 2, 3, 4 or 5 wherein R¹And R¹' independently is C₄-C₄₀A cyclic tertiary hydrocarbon group.

7. The catalyst compound of paragraph 1, 2, 3, 4, 5 or 6 wherein R¹And R¹' independently is C₄-C₄₀Polycyclic tertiary hydrocarbon groups.

8. The catalyst compound of any of paragraphs 1-7, wherein each X is independently selected from the group consisting of: substituted or unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, hydrogen groups, amino groups, alkoxy groups, thio groups, phosphorus groups, halo groups, and combinations thereof (two X's may form part of a fused ring or ring system).

9. The catalyst compound of any of paragraphs 1-8, wherein each L is independently selected from the group consisting of: ethers, thioethers, amines, phosphines, diethyl ether, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, alkenes, alkynes, allenes, and carbenes, and combinations thereof, optionally, two or more L may be formed as part of a fused ring or ring system).

10. The catalyst compound of paragraph 1 wherein M is Zr or Hf, Q is nitrogen, A¹And A¹'are both carbon, E and E' are both oxygen, and R¹And R¹' all are C₄-C₂₀A cyclic tertiary alkyl group.

11. The catalyst compound of paragraph 1 wherein M is Zr or Hf, Q is nitrogen, A¹And A¹'are both carbon, E and E' are both oxygen, and R¹And R¹' are all adamantan-1-yl or substituted adamantan-1-yl.

12. The catalyst compound of paragraph 1 wherein M is Zr or Hf, Q is nitrogen, A¹And A¹'are both carbon, E and E' are both oxygen, and R¹And R¹' all are C₆-C₂₀And (4) an aryl group.

13. The catalyst compound of paragraph 1 wherein Q is nitrogen and A¹And A¹' are all carbon, R¹And R¹'both are hydrogen, E and E' are both NR⁹Wherein R is⁹Is selected from C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl or heteroatom containing groups.

14. The catalyst compound of paragraph 1 wherein Q is carbon and A¹And A¹'both are nitrogen, and E' are both oxygen.

15. The catalyst compound of paragraph 1 wherein Q is carbon and A¹Is nitrogen, A¹' is C (R)²²) And E' are both oxygen, wherein R²²Selected from hydrogen, C₁-C₂₀Hydrocarbyl radical, C₁-C₂₀A substituted hydrocarbyl group.

16. The catalyst compound of paragraph 1 wherein said heterocyclic lewis base is selected from the group represented by the formula:

wherein each R²³Independently selected from hydrogen, C₁-C₂₀Alkyl and C₁-C₂₀A substituted alkyl group.

17. The catalyst compound of paragraph 2 wherein M is Zr or Hf, E and E' are both oxygen, and R ¹And R¹' both are C4-C20 cyclic tertiary alkyl groups.

18. The catalyst compound of paragraph 2 wherein M is Zr or Hf, E and E' are both oxygen, R¹And R¹' are both adamantan-1-yl or substituted adamantan-1-yl.

19. The catalyst compound of paragraph 2 wherein M is Zr or Hf, E and E' are both oxygen, and R¹、R¹'、R³And R³Each of' is an adamantan-1-yl or substituted adamantan-1-yl group.

20. The catalyst compound of paragraph 2 wherein M is Zr or Hf, E and E' are both oxygen, R¹And R¹' all are C₄-C₂₀Cyclic tertiary alkyl radical, and R⁷And R⁷' all are C₁-C₂₀An alkyl group.

21. The catalyst compound of paragraph 2 wherein M is Zr or Hf, E and E' are both O, R¹And R¹' all are C₄-C₂₀Cyclic tertiary alkyl radical, and R⁷And R⁷' all are C₁-C₂₀An alkyl group.

22. The catalyst compound of paragraph 2 wherein M is Zr or Hf, E and E' are both O, R¹And R¹' all are C₄-C₂₀Cyclic tertiary alkyl radical, and R⁷And R⁷' all are C₁-C₃An alkyl group.

23. The catalyst compound of paragraph 1, wherein the catalyst compound is represented by one or more of the following formulas:

24. a catalyst system comprising an activator and the catalyst compound of any of stages 1-23.

25. The catalyst system of paragraph 24, wherein the activator comprises an alumoxane or a non-coordinating anion.

26. The catalyst system of paragraph 24, wherein the activator is soluble in a non-aromatic hydrocarbon solvent.

27. The catalyst system of paragraph 24, wherein the catalyst system is free of aromatic solvents.

28. The catalyst system of paragraph 24, wherein the activator is represented by the formula:

(Z)_d ⁺(A^d-)

wherein Z is (L-H) or a reducible Lewis acid, L is a neutral Lewis base; h is hydrogen; (L-H)⁺Is a bronsted acid; a. the^d-Is a non-coordinating anion having a charge d-; d is an integer of 1 to 3.

29. The catalyst system of paragraph 24, wherein the activator is represented by the formula:

wherein: e is nitrogen or phosphorus; d is 1, 2 or 3; k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6;

n-k＝d；R^1′、R^2′and R^3′Independently C optionally substituted by one or more alkoxy, silyl, halogen atoms or halogen-containing groups₁-C₅₀A hydrocarbon group, wherein R^1′、R^2′And R^3′Together containing 15 or more carbon atoms; mt is an element selected from group 13 of the periodic table; and each Q is independently hydrogen, a bridged or unbridged dialkylamido, halo, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halo-substituted hydrocarbyl group.

30. The catalyst system of paragraph 24, wherein the activator is represented by the formula:

(Z)_d ⁺(A^d-)

wherein A is^d-Is a non-coordinating anion having a charge d-; d is an integer from 1 to 3, (Z) _d ⁺Represented by one or more of the following formulae:

31. the catalyst system of paragraph 24, wherein the activator is one or more of the following:

N-methyl-4-nonadecyl-N-octadecylanilinium tetrakis (pentafluorophenyl) borate,

N-methyl-4-nonadecyl-N-octadecylanilinium tetrakis (perfluoronaphthyl) borate,

dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate,

dioctadecyl methylammonium tetrakis (perfluoronaphthyl) borate,

n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

triphenylcarbenium tetrakis (pentafluorophenyl) borate

Trimethyl ammonium tetrakis (perfluoronaphthyl) borate,

triethylammonium tetrakis (perfluoronaphthyl) borate,

tripropylammonium tetrakis (perfluoronaphthyl) borate,

tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate,

tri (tert-butyl) ammonium tetrakis (perfluoronaphthyl) borate,

n, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate,

n, N-diethylanilinium tetrakis (perfluoronaphthyl) borate,

n, N-dimethyl- (2,4, 6-trimethylanilinium) tetrakis (perfluoronaphthyl) borate,

tetrakis (perfluoronaphthyl) boronic acid

(tropylium)，

Triphenylcarbon tetrakis (perfluoronaphthyl) borate

Tetrakis (perfluoronaphthyl) borate triphenylphosphine

Tetrakis (perfluoronaphthyl) borate triethylsilane

Tetrakis (perfluoronaphthyl) boratabenzene (diazo)

)，

Trimethyl ammonium tetrakis (perfluorobiphenyl) borate,

Triethylammonium tetra (perfluorobiphenyl) borate,

Tripropylammonium tetrakis (perfluorobiphenyl) borate,

Tri (n-butyl) ammonium tetra (perfluorobiphenyl) borate,

Tri (tert-butyl) ammonium tetrakis (perfluorobiphenyl) borate,

n, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate,

N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate,

N, N-dimethyl- (2,4, 6-trimethylphenylammonium) tetrakis (perfluorobiphenyl) borate,

Tetra (perfluorobiphenyl) boronic acid

Triphenylcarbon tetrakis (perfluorobiphenyl) borate

Tetrakis (perfluorobiphenyl) borate triphenylphosphine

Tetrakis (perfluorobiphenyl) boronic acid triethylsilane

Tetrakis (perfluorobiphenyl) borate benzene (diazonium)

)，

[ 4-tert-butyl-PhNMe 2H ] [ (C6F3(C6F5)2)4B ],

the reaction product of trimethyl ammonium tetraphenyl borate,

triethylammonium tetraphenylborate,

Tripropylammonium tetraphenyl borate, the process for the preparation of the compound,

tri (n-butyl) ammonium tetraphenyl borate,

tri (tert-butyl) ammonium tetraphenylborate,

n, N-dimethylanilinium tetraphenylborate,

n, N-diethylanilinium tetraphenylborate,

n, N-dimethyl- (2,4, 6-trimethylanilinium) tetraphenylborate,

tetraphenylboronic acids

Triphenylcarbon tetraphenylborate

Tetraphenylboronic acid triphenylphosphine

Tetraphenylboronic acid triethylsilane

Tetraphenylboronic acid benzene (diazo)

)，

Trimethyl ammonium tetrakis (pentafluorophenyl) borate,

Triethylammonium tetrakis (pentafluorophenyl) borate,

tripropylammonium tetrakis (pentafluorophenyl) borate,

tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate,

tris (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate,

n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

n, N-diethylanilinium tetrakis (pentafluorophenyl) borate,

n, N-dimethyl- (2,4, 6-trimethylanilinium) tetrakis (pentafluorophenyl) borate,

tetrakis (pentafluorophenyl) borate

Triphenylcarbenium tetrakis (pentafluorophenyl) borate

Triphenylphosphine tetrakis (pentafluorophenyl) borate

Triethylsilane tetrakis (pentafluorophenyl) borate

Tetrakis (pentafluorophenyl) borate benzene (diazo)

)，

Trimethylammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

triethylammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

tripropylammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

tri (n-butyl) ammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

dimethyl (tert-butyl) ammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

n, N-dimethylanilinium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

n, N-diethylanilinium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

n, N-dimethyl- (2,4, 6-trimethylanilinium) tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

tetrakis (2,3,4, 6-tetrafluorophenyl) boronic acid

Triphenylcarbenium tetrakis (2,3,4, 6-tetrafluorophenyl) borate

Tetra (2,3,4, 6-tetrafluorobenzene)Radical) boric acid triphenylphosphine

Triethylsilane tetrakis (2,3,4, 6-tetrafluorophenyl) borate

Tetrakis (2,3,4, 6-tetrafluorophenyl) borate benzene (diazonium)

)，

Trimethylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

triethylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

tripropylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

tri (n-butyl) ammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

Tri (tert-butyl) ammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

n, N-dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

N, N-diethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

N, N-dimethyl- (2,4, 6-trimethylanilinium) tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

Triphenylcarbenium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

Tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate triphenylphosphine

Triethylsilane tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

Tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate benzene (diazonium)

)，

Di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate,

dicyclohexylammonium tetrakis (pentafluorophenyl) borate,

tris (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate

Tris (2, 6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate

Triphenylcarbenium tetrakis (perfluorophenyl) borate

1- (4- (tris (pentafluorophenyl) boronic acid) -2,3,5, 6-tetrafluorophenyl) pyrrolidine

Tetrakis (pentafluorophenyl) borate,

4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluoropyridine, and

triphenylcarbenium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

32. A process for polymerizing olefins comprising contacting one or more olefins with the catalyst system of any of stages 23-31.

33. The process of paragraph 32, wherein said process is conducted at a temperature of from about 0 ℃ to about 300 ℃, at a pressure of from about 0.35MPa to about 10MPa, and for a time of up to 300 minutes.

34. The method of paragraph 32, further comprising obtaining a polymer.

35. The process of paragraph 32, wherein said olefin comprises one or more substituted or unsubstituted C₂-C₄₀An alpha-olefin.

Experiment of

Scheme 3 shows a diagram of catalyst complexes 1-32. Complexes 26 and 27 were prepared as described in U.S. patent application serial No. entitled "Lewis base catalysts and methods thermal of" (attorney docket No. 2019EM043), filed concurrently, which claims priority and benefit of 62/804,372 filed on 12/2/2019. Complex 28 (comparative) was prepared as described by Golisz et al (2009) Macromolecules, v.42, pp.8751-8762 and is a comparative complex. Complexes 31 and 32 were prepared using a procedure similar to that described for complex 29. 2- (Adamantan-1-yl) -4- (tert-butyl) phenol was prepared from 4-tert-butylphenol (Merck) and adamantanol-1 (Aldrich) as described in Organic Letters 2015, v.17, pp.2242-2245.

Scheme 3

Scheme 3 (continue)

Scheme 3 (continue)

Scheme 3 (continue)

2- (adamantan-1-yl) -6-bromo-4- (tert-butyl) phenol

To a solution of 57.6g (203mmol) of 2- (adamantan-1-yl) -4- (tert-butyl) phenol in 400mL of chloroform was added dropwise a solution of 10.4mL (203mmol) of bromine in 200mL of chloroform at room temperature for 30 minutes. The resulting mixture was diluted with 400mL of water. The resulting mixture was extracted with dichloromethane (3X 100mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried and then evaporated to dryness. 71.6g (97%) of a white solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.32(d,J＝2.3Hz,1H),7.19(d,J＝2.3Hz,1H),5.65(s,1H),2.18-2.03(m,9H),1.78(m,6H),1.29(s,9H)。¹³C NMR(CDCl₃,100MHz):δ148.07,143.75,137.00,126.04,123.62,112.11,40.24,37.67,37.01,34.46,31.47,29.03。

(1- (3-bromo-5- (tert-butyl) -2- (methoxymethoxy) phenyl) adamantane

To a solution of 71.6g (197mmol) of 2- (adamantan-1-yl) -6-bromo-4- (tert-butyl) phenol in 1,000mL of THF at room temperature was added portionwise 8.28g (207mmol, 60% by weight in mineral oil) of sodium hydride. To the resulting suspension was added dropwise 16.5mL (217mmol) of methoxymethyl chloride at room temperature over 10 minutes. The resulting mixture was stirred overnight and then poured into 1,000ml of water. The resulting mixture was extracted with dichloromethane (3X 300mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried and then evaporated to dryness. 80.3g (. about.quant.) of a white solid were obtained. ¹H NMR(CDCl₃,400MHz):δ7.39(d,J＝2.4Hz,1H),7.27(d,J＝2.4Hz,1H),5.23(s,2H),3.71(s,3H),2.20-2.04(m,9H),1.82-1.74(m,6H),1.29(s,9H)。¹³C NMR(CDCl₃,100MHz):δ150.88,147.47,144.42,128.46,123.72,117.46,99.53,57.74,41.31,38.05,36.85,34.58,31.30,29.08。

2- (3-Adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane (dioxaborolan)

To a solution of 22.5g (55.0mmol) (1- (3-bromo-5- (tert-butyl) -2- (methoxymethoxy) phenyl) adamantane in 300mL anhydrous THF at-80 deg.C was added dropwise 23.2mL (57.9mmol, 2.5M) nBuLi in hexane for 20 min the reaction mixture was stirred at that temperature for 1 h, then 14.5mL (71.7mmol) 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolane was added the resulting suspension stirred at room temperature for 1 h, then poured into 300mL water the resulting mixture was extracted with dichloromethane (3X 300mL), the combined organic extracts were extracted over Na₂SO₄Dried and then evaporated to dryness. 25.0g (. about.quantitative) of a colorless viscous oil was obtained.¹H NMR(CDCl₃,400MHz):δ7.54(d,J＝2.5Hz,1H),7.43(d,J＝2.6Hz,1H),5.18(s,2H),3.60(s,3H),2.24-2.13(m,6H),2.09(br.s.,3H),1.85-1.75(m,6H),1.37(s,12H),1.33(s,9H)。¹³C NMR(CDCl₃,100MHz):δ159.64,144.48,140.55,130.58,127.47,100.81,83.48,57.63,41.24,37.29,37.05,34.40,31.50,29.16,24.79。

1- (2 '-bromo-5- (tert-butyl) -2- (methoxymethoxy) - [1,1' -biphenyl ] -3-yl) adamantane

To a solution of 25.0g (55.0mmol) of 2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 200mL of bis (borolan-A-ethyl) silane

To the solution in the alkane were added 15.6g (55.0mmol) of 2-bromoiodobenzene, 19.0g (137mmol) of potassium carbonate and 100mL of water in this order. Mixing the obtained mixture The mixture was purged with argon for 10 minutes, and then 3.20g (2.75mmol) of Pd (PPh) was added₃)₄. The mixture thus obtained was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The resulting mixture was extracted with dichloromethane (3X 100mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-dichloromethane ═ 10:1 by volume). 23.5g (88%) of a white solid were obtained.¹H NMR(CDCl₃,400MHz):δ7.68(dd,J＝1.0,8.0Hz,1H),7.42(dd,J＝1.7,7.6Hz,1H),7.37-7.32(m,2H),7.20(dt,J＝1.8,7.7Hz,1H),7.08(d,J＝2.5Hz,1H),4.53(d,J＝4.6Hz,1H),4.40(d,J＝4.6Hz,1H),3.20(s,3H),2.23-2.14(m,6H),2.10(br.s.,3H),1.86-1.70(m,6H),1.33(s,9H)。¹³C NMR(CDCl₃,100MHz):δ151.28,145.09,142.09,141.47,133.90,132.93,132.41,128.55,127.06,126.81,124.18,123.87,98.83,57.07,41.31,37.55,37.01,34.60,31.49,29.17。

2- (3'- (adamantan-1-yl) -5' - (tert-butyl) -2'- (methoxymethyloxy) - [1,1' -biphenyl ] -2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane

To 30.0g (62.1mmol) of 1- (2 '-bromo-5- (tert-butyl) -2- (methoxymethoxy) - [1,1' -biphenyl at-80 deg.C]-3-yl) adamantane to a solution in 500mL anhydrous THF was added dropwise 25.6mL (63.9mmol, 2.5M) of a solution of nBuLi in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 16.5mL (80.7mmol) 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 and then poured into 300ml of water. The resulting mixture was extracted with dichloromethane (3X 300mL) and the combined organic extracts were washed with Na ₂SO₄Dried and then evaporated to dryness. 32.9g (. about.quantitative) of a colorless glassy solid was obtained.¹H NMR(CDCl₃,400MHz):δ7.75(d,J＝7.3Hz,1H),7.44-7.36(m,1H),7.36-7.30(m,2H),7.30-7.26(m,1H),6.96(d,J＝2.4Hz,1H),4.53(d,J＝4.7Hz,1H),4.37(d,J＝4.7Hz,1H),3.22(s,3H),2.26-2.14(m,6H),2.09(br.s.,3H),1.85-1.71(m,6H),1.30(s,9H),1.15(s,6H),1.10(s,6H)。¹³C NMR(CDCl₃,100MHz):δ151.35,146.48,144.32,141.26,136.15,134.38,130.44,129.78,126.75,126.04,123.13,98.60,83.32,57.08,41.50,37.51,37.09,34.49,31.57,29.26,24.92,24.21。

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

To a solution of 32.9g (62.0mmol) of 2- (3'- (adamantan-1-yl) -5' - (tert-butyl) -2'- (methoxymethoxy) - [1,1' -biphenyl]-2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 140ml of bis

To the solution in the alkane were added 7.35g (31.0mmol) of 2, 6-dibromopyridine, 50.5g (155mmol) of cesium carbonate and 70ml of water in this order. The resulting mixture was purged with argon for 10 minutes, and then 3.50g (3.10mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. To the resulting oil were then added 300mL THF, 300mL methanol, and 21mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 500mL of water. The resulting mixture was extracted with dichloromethane (3X 350mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried 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, vol). The glassy solid obtained was triturated with 70ml of n-pentane and the precipitate obtained was filtered off, washed with 2X 20ml of n-pentane and dried in vacuo. This gave 21.5g (87% ) A mixture of the two isomers as a white powder.¹H NMR(CDCl₃,400MHz):δ8.10+6.59(2s,2H),7.53-7.38(m,10H),7.09+7.08(2d,J＝2.4Hz,2H),7.04+6.97(2d,J＝7.8Hz,2H),6.95+6.54(2d,J＝2.4Hz),2.03-1.79(m,18H),1.74-1.59(m,12H),1.16+1.01(2s,18H)。¹³C NMR(CDCl₃100MHz, shift of minor isomers labeled with:) # 157.86,157.72, 150.01,149.23, 141.82, 141.77,139.65, 139.42,137.92,137.43,137.32, 136.80,136.67, 136.29, 131.98, 131.72,130.81,130.37, 129.80,129.09, 128.91,128.81, 127.82, 127.67,126.40,125.65, 122.99, 122.78,122.47,122.07, 40.48,40.37, 37.04,36.89, 34.19, 34.01,31.47,29.12, 29.07.

Hafnium dimethyl [2', 2' - (pyridine-2, 6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-phenate) ] (Complex 5)

3.22g (10.05mmol) of hafnium tetrachloride (F) are introduced at 0 ℃ by syringe<0.05% Zr) to a suspension in 250mL of anhydrous toluene 14.6mL (42.2mmol, 2.9M) of MeMgBr in ether were added in one portion. The resulting suspension was stirred for 1 min and 8.00g (10.05mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl were added portionwise over 1 min]-2-phenol). The reaction mixture was stirred at room temperature for 36 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 100mL of hot toluene and the combined organic extracts were filtered through a pad of Celite (Celite) 503. The filtrate was then evaporated to dryness. The residue was triturated with 50mL of n-hexane, the precipitate obtained was filtered off (G3), washed with 20mL of n-hexane (2X 20mL) and then dried in vacuo. 6.66g (61%, 1:1 solvate with n-hexane) of a pale beige solid are produced. C ₅₉H₆₉HfNO₂×1.0(C₆H₁₄) Analytical calculation of (a): c, 71.70; h, 7.68; n, 1.29. Measured value: c71.95; h, 7.83; and (4) N1.18.¹H NMR(C₆D₆,400MHz):δ7.58(d,J＝2.6Hz,2H),7.22-7.17(m,2H),7.14-7.08(m,4H),7.07(d,J＝2.5Hz,2H),7.00-6.96(m,2H),6.48-6.33(m,3H),2.62-2.51(m,6H),2.47-2.35(m,6H),2.19(br.s,6H),2.06-1.95(m,6H),1.92-1.78(m,6H),1.34(s,18H),-0.12(s,6H)。¹³C NMR(C₆D₆,100MHz):δ159.74,157.86,143.93,140.49,139.57,138.58,133.87,133.00,132.61,131.60,131.44,127.98,125.71,124.99,124.73,51.09,41.95,38.49,37.86,34.79,32.35,30.03。

Zirconium dimethyl [2', 2' - (pyridine-2, 6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-phenate) ] (Complex 6)

To a suspension of 2.92g (12.56mmol) of zirconium tetrachloride in 300mL of dry toluene at 0 ℃ was added 18.2mL (52.7mmol, 2.9M) of MeMgBr in ether in one portion by syringe. To the resulting suspension was immediately added 10.00g (12.56mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 2 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 100mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 50mL of n-hexane and the precipitate obtained was filtered off (G3), washed with n-hexane (2X 20mL) and then dried in vacuo. 8.95g (74%, 1:0.5 solvate with n-hexane) of a beige solid are obtained. C₅₉H₆₉ZrNO₂×0.5(C₆H₁₄) Analytical calculation of (a): c, 77.69; h, 7.99; n,1.46. found: c77.90; h, 8.15; and N is 1.36. ¹H NMR(C₆D₆,400MHz):δ7.56(d,J＝2.6Hz,2H),7.20-7.17(m,2H),7.14-7.07(m,4H),7.07(d,J＝2.5Hz,2H),6.98-6.94(m,2H),6.52-6.34(m,3H),2.65-2.51(m,6H),2.49-2.36(m,6H),2.19(br.s.,6H),2.07-1.93(m,6H),1.92-1.78(m,6H),1.34(s,18H),0.09(s,6H)。¹³C NMR(C₆D₆,100MHz):δ159.20,158.22,143.79,140.60,139.55,138.05,133.77,133.38,133.04,131.49,131.32,127.94,125.78,124.65,124.52,42.87,41.99,38.58,37.86,34.82,32.34,30.04。

1-adamantanol

To a stirred solution of 1-bromoadamantane (5.00g, 23.242mmol) in dimethylmethylamino (25ml) was added hydrochloric acid (8.7ml of 0.67M HCl), followed by water (15 ml). The mixture was brought to 105 ℃ and stirred for 1 hour. After cooling to room temperature, water (150mL) was added and the resulting precipitate was collected by vacuum filtration. The solid was dissolved in dichloromethane (200ml) and washed with water (3X 100 ml). The organic layer was dried (MgSO₄) Filtered and concentrated in vacuo to give 3.512g (23.069mmol, 99% yield).

2, 4-bis (adamantan-1-yl) phenol

To a mixture of phenol (2.00g, 21.252mmol) and 1-adamantanol (6.794g, 44.629mmol, 2.10 equiv.) in dichloromethane (20mL) was added concentrated sulfuric acid (2.5mL) dropwise over 10 min at room temperature. It was stirred at room temperature overnight. Water (15ml) was added to the reaction mixture to bring the pH to 9-10(2M aqueous NaOH). The organics were extracted with dichloromethane (3X 20ml), washed with brine and dried (MgSO)₄) Filtered and concentrated in vacuo. The residue was purified by column chromatography (5-10% ethyl acetate/hexanes) to give 1.29g (17% yield) of a white solid.

1,1' - (4- (methoxymethyloxy) -1, 3-phenylene) bis (adamantane)

To a mixture of 2, 4-bis (adamantyl) phenol (1.29g, 3.558mmol) in tetrahydrofuran (3mL) was slowly added 60% sodium hydride in mineral oil (0.185g, 4.625mmol, 1.30 equiv). This was stirred at room temperature for 30 minutes, at which time chloromethyl methyl ether (0.459mL, 6.049mmol, 1.70 equiv.) was added gradually. The reaction was stirred at room temperature overnight. The reaction mixture was quenched with water (20mL) and the pH was adjusted to 8-10 using potassium hydroxide. The product was extracted with diethyl ether (3X 30ml) and dried (MgSO)₄) Filtered and concentrated in vacuo to give 1.330g (3.275mmol, 92% yield).

(3, 5-Diadamantan-1-yl) -2- (methoxymethoxy) phenyl) lithium (1, 2-dimethoxyethane)

Pentane (20mL) was added to 1,1' - (4- (methoxymethyloxy) -1, 3-phenylene) bis (adamantane) (1.38g, 3.40mmol) to form a solution. A1.6M solution of BuLi in hexane (2.13mL, 3.40mmol) was added dropwise. 1, 2-Dimethoxyethane (DME) was then added dropwise. Within a few minutes, the yellow solution became cloudy and then a precipitate began to form. The mixture was stirred for 1.5 hours, then the precipitate was separated on a sinter dish, washed with pentane (3X 15mL) and dried under reduced pressure. The product was isolated as an off-white solid. Yield: 1.15g, 67.2%.

1,1' - (2' -bromo-2- (methoxymethyloxy) - [1,1' -biphenyl ] -3, 5-diyl) bis (adamantane)

Toluene (20mL) was added to (3, 5-diamantan-1-yl) -2- (methoxymethoxy) phenyl) lithium (1, 2-dimethoxyethane) (1.15g, 2.29mmol) to form a suspension. A solution of 1-bromo-2-chlorobenzene (0.482g, 2.52mmol) in toluene (10mL) was added dropwise over 1 hour to form a cloudy solution. The mixture was stirred for a further 1 hour, and then the volatiles were removed under reduced pressure. The residue is treated with CH ₂Cl₂Extracted (8mL) and filtered through Celite 503 on a Teflon filter. The volatiles were evaporated and pentane (3mL) was added to the residue. The mixture was cooled to-20 ℃ overnight. Without crystallization, so volatiles are evaporatedAnd the residue was dried under reduced pressure at 60 ℃. Yield: 1.32g, 98.9%.

2', 2' - (pyridine-2, 6-diyl) bis ((3, 5-diamantan-1-yl) - [1,1' -biphenyl ] -2-ol)

Tetrahydrofuran (15mL) was added to 1,1' - (2' -bromo-2- (methoxymethyloxy) - [1,1' -biphenyl]3, 5-diyl) bis (adamantane) (1.32g, 2.26mmol) to form a solution. The mixture was cooled to-45 ℃ and a 1.6M solution of BuLi in hexane (1.46mL, 2.33mmol) was added dropwise over one minute. The mixture was allowed to slowly warm to-25 ℃ over 45 minutes. Adding solid ZnCl into the clarified solution₂(0.216g, 1.58 mmol). The mixture was allowed to warm slowly to ambient temperature over 30 minutes. After 30 minutes at ambient temperature, 2, 6-dibromopyridine (0.260g, 1.10mmol) and Pd (P (tBu)₃)₂(0.023g, 0.045mmol) was added to the clear colorless solution. The mixture was heated overnight on a metal block maintained at 65 ℃. After stirring overnight, the volatiles were evaporated with a rotary evaporator. To the residue were added methanol (20mL), THF (20mL) and concentrated HCl (1 mL). The mixture was heated to 60 ℃ for 5 hours. The volatiles were then evaporated with a rotary evaporator and CH ₂Cl₂The residue was extracted (60 mL). The organics were washed with water (3X 50mL) and diluted NaHCO₃The pH was adjusted to 7 (1X 50mL), then dried with brine (40mL) and MgSO₄And (5) drying. Filtration and removal of volatiles gave 1.2g of crude product. Purify by column chromatography on silica gel using 2-8% EtOAc in isohexane. Evaporation of isohexane-EtOAc gave a white residue containing some CH insolubility₂Cl₂The substance of (1). The solid was extracted with benzene (10mL), filtered and evaporated. The residue was dried at 60 ℃ under reduced pressure to give a foamy solid. Yield: 0.322g, 30.8%.

Dibenzylzirconium [2', 2' - (pyridine-2, 6-diyl) bis (3, 5-diamantan-1-yl) - [1,1' -biphenyl ] -2-phenate) ] (Complex 22)

Benzene (15mL) was added to 2', 2' - (pyridine-2, 6-diyl) bis((3, 5-diamantan-1-yl) - [1,1' -biphenyl)]-2-phenol) (0.315g, 0.331mmol) to form a solution. Adding ZrBn₄(0.151g, 0.331mmol) and benzene (2 mL). The mixture was shaken to form a yellow-orange solution. After 30 min, the mixture was filtered and evaporated to 1 mL. Hexane (3mL) was added to form a turbid mixture. The volatiles were evaporated to dryness. The yellow-orange solid was washed thoroughly with pentane (5 mL). The pentane extract was filtered and cooled to-20 ℃ for several hours. Some yellow solid was isolated from the pentane solution. The sample that had been washed with pentane was combined with methylcyclohexane (10mL) and the mixture was heated to near boiling for several minutes. Some crystalline solid was isolated from the orange solution. The mixture was allowed to stand at ambient temperature for 2 hours, and then a colorless solid was separated and dried under reduced pressure. The HNMR spectrum showed that the product co-crystallized with 1 equivalent of methylcyclohexane. Yield: 0.092g, 21%.

1- (3-bromo-2- (methoxymethoxy) -5-methylphenyl) adamantane

To a solution of 21.3g (66.4mmol) of 2-bromo-6-adamantyl-4-methylphenol in 300mL of anhydrous THF at room temperature was added in portions 2.79g (69.7mmol, 60% by weight in mineral oil) of sodium hydride. Thereafter, 5.55mL (73.0mmol) of MOMCl was added dropwise over 1 hour. The reaction mixture was heated at 60 ℃ for 24 hours and then poured into 300mL of cold water. The crude product was extracted with 3X 200mL of dichloromethane. The combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. 24.3g (quantitative) of a colorless oil were obtained.¹H NMR(CDCl₃,400MHz):δ7.24(d,J＝1.5Hz,1H),7.05(d,J＝1.8Hz,1H),5.22(s,2H),3.71(s,3H),2.27(s,3H),2.07-2.15(m,9H),1.78(m,6H)。¹³C 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。

2- (3-adamantan-1-yl) -2- (methoxymethoxy) -5-methylphenyl) benzo [ b ] thiophene

To a solution of 10.0g (74.5mmol) of benzo [ b ] at-10 deg.C]Thiophene in 250mL dry THF solution in 29.8mL (74.5mmol, 2.5M) nBuLi in hexane was added dropwise. The reaction mixture was stirred at 0 ℃ for 1 hour, then 11.2g (82.0mmol) ZnCl was added₂. Next, the resulting solution was warmed to room temperature, followed by addition of 13.6g (37.3mmol) of 1- (3-bromo-2- (methoxymethoxy) -5-methylphenyl) adamantane and 1.52g (2.98mmol) of Pd [ P ]^tBu₃]₂. The resulting mixture was stirred at 60 ℃ overnight and then poured into 250mL of water. The crude product was extracted with 3X 150mL of dichloromethane. The combined organic extracts were washed with Na ₂SO₄Dried 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, vol). 5.31g (34%) of a pale yellow solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.88(d,J＝7.7Hz,1H),7.81(d,J＝7.4Hz,1H),7.54(s,1H),7.32-7.42(m,2H),7.18-7.23(m,2H),4.79(s,2H),3.49(s,3H),2.38(s,3H),2.24(m,6H),2.16(m,3H),1.85(m,6H)。

3-bromo-2- (3-adamantan-1-yl) -2- (methoxymethoxy) -5-methylphenyl) benzo [ b ] thiophene

To 5.31g (12.7mmol) of 2- (3-adamantan-1-yl) -2- (methoxymethoxy) -5-methylphenyl) benzo [ b ] at room temperature]To a solution of thiophene in 150ml chloroform was added 2.26g (12.7mmol) of N-bromosuccinimide. The reaction mixture was stirred at this temperature for 2 hours and then poured into 100mL of water. The crude product was extracted with 3X 50mL of dichloromethane. The combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was recrystallized from 90mL of n-hexane at-30 ℃. 6.25g (98%) of a pale yellow solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.90(d,J＝7.8Hz,1H),7.84(d,J＝7.9Hz,1H),7.49(dt,J＝0.9,7.1Hz,1H),7.43(dt,J＝1.2,8.1Hz,1H),7.24(d,J＝2.0Hz,1H),7.12(d,J＝1.7Hz,1H),4.66(s,2H),3.33(s,3H),2.38(s,3H),2.22(m,6H),2.14(br.s,3H),1.83(m,6H)。¹³C NMR(CDCl₃,100MHz):δ153.19,143.13,138.54,138.19,137.38,132.48,130.68,129.30,126.06,125.38,125.03,123.42,122.19,107.76,99.33,57.38,41.17,37.30,36.97,29.10,20.98。

6,6' - (pyridine-2, 6-diylbis (benzo [ b ] thiophene-3, 2-diyl)) bis (2-adamantan-1-yl) -4-methylphenol)

To a solution of 3.00g (6.03mmol) of 3-bromo-2- (3-adamantan-1-yl) -2- (methoxymethoxy) -5-methylphenyl) benzo [ b ] at-80 deg.C]Thiophene to a solution of 120mL dry THF was added dropwise a solution of 2.41mL (6.03mmol, 2.5M) nBuLi in hexane. The reaction mixture is stirred at this temperature for 30 minutes, then 2.32g (17.1mmol) of ZnCl are added ₂. The resulting mixture was warmed to room temperature, and then 0.72g (3.02mmol) of 2, 6-dibromopyridine and 245mg (0.48mmol) of Pd [ P ] were added successively^tBu₃]₂. The resulting mixture was stirred at 60 ℃ overnight, poured into 100mL of water, and the crude product was extracted with dichloromethane (3X 50 mL). The combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 1mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The resulting mixture was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate-triethylamine ═ 100:10:1, volume). 0.78g (31%) of a white foam are obtained.¹H NMR(CDCl₃,400MHz):δ7.87-7.94(m,4H),7.67(t,J＝7.8Hz,1H),7.38-7.48(m,4H),7.28(d,J＝7.8Hz,2H),6.91-6.99(m,4H),2.23(s,6H),1.82(br.s,6H),1.67(br.s,9H),1.57-1.62(m,6H),1.42-1.50(m,6H)。¹³C NMR(CDCl₃,100MHz):δ153.56,150.70,140.51,139.91,138.86,138.50,137.87,131.91,129.49,128.68,128.49,124.92,124.77,123.71,122.82,122.00,40.02,36.81,36.60,28.98,20.73。

Hafnium dimethyl [6,6' - (pyridine-2, 6-diyl bis (benzo [ b ]))]Thiophene-3, 2-diyl)) bis (2-adamantan-1-yl) -4-methylphenoxide salt)](Complex 23). To a suspension of 155mg (0.485mmol) hafnium tetrachloride in 50mL dry toluene at room temperature was added 0.75mL (2.20mmol, 2.9M) MeMgBr in ether in one portion. The resulting suspension was stirred for 1 minute, and 400mg (0.485mmol) of 6,6' - (pyridine-2, 6-diylbis (benzo [ b ] was added dropwise within 1 minute ]Thiophene-3, 2-diyl)) bis (2-adamantan-1-yl) -4-methylphenol) in 10mL of anhydrous toluene. The reaction mixture was stirred at room temperature overnight and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The resulting solid was washed with 5mL of n-hexane and dried under vacuum. 303mg (60%) of a beige solid were obtained as hexane solvate. C₅₇H₅₇HfNO₂S₂×2(C₆H₁₄) Analytical calculation of (a): c, 68.89; h, 7.12; and N, 1.16. Measured value: c69.07; h7.33; and N is 1.11.¹H NMR(C₆D₆,400MHz):δ7.35(dd,J＝1.9,6.9Hz,2H),7.21(d,J＝2.1Hz,2H),7.12(d,J＝2.1Hz,2H),7.05-7.12(m,4H),6.92(dd,J＝2.0,6.5Hz,2H),6.69(t,J＝7.8Hz,1H),6.46(d,J＝7.8Hz,2H),2.20(s,6H),2.11-2.17(m,6H),1.99-2.07(m,6H),1.75-1.87(m,12H),1.63-1.70(m,6H),0.18(s,6H)。¹³C NMR(C₆D₆,100MHz):δ160.12,154.44,150.43,149.60,147.46,143.70,141.40,140.26,134.21,131.01,130.32,129.66,127.31,126.59,125.59,125.45,124.83,124.64,122.98,122.68,114.02,52.62,41.19,38.05,37.67,32.30,29.73,23.39,14.69。

Zirconium dimethyl [6,6' - (pyridine-2, 6-diyl bis (benzo [ b ] thiophene-3, 2-diyl)) bis (2-adamantan-1-yl) -4-methylphenoxide) ] (Complex 24)

To a suspension of 58mg (0.247mmol) zirconium tetrachloride in 30mL of dry toluene at room temperature was added 0.38mL (1.11mmol, 2.9M) of MeMgBr in one portionAnd (4) ether solution. The resulting suspension was stirred for 10 seconds and 204mg (0.247mmol) of 6,6' - (pyridine-2, 6-diylbis (benzo [ b ] was added dropwise within 30 seconds]Thiophene-3, 2-diyl)) bis (2-adamantan-1-yl) -4-methylphenol) in 10mL of anhydrous toluene. The reaction mixture was stirred at room temperature overnight and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The resulting solid was washed with 5mL of n-hexane and then dried under vacuum. 140mg (60%) of a beige solid are obtained. C ₅₇H₅₇ZrNO₂S₂Analytical calculation of (a): c, 72.57; h, 6.09; n, 1.48. Measured value: c72.78; h6.29; n1.31.¹H NMR(C₆D₆,400MHz):δ7.34(dd,J＝1.9,6.7Hz,2H),7.20(d,J＝2.2Hz,2H),7.12(d,J＝2.5Hz,2H),7.08(m,4H),7.02(m,2H),6.91(dd,J＝1.8,6.4Hz,2H),6.69(t,J＝7.6Hz,1H),6.45(d,J＝7.8Hz,2H),2.20(s,6H),2.15-2.21(m,6H),2.02-2.09(m,6H),1.75-1.85(m,12H),1.64-1.72(m,6H),0.40(s,6H)。¹³C NMR(C₆D₆,100MHz):δ160.18,155.17,149.57,141.60,140.66,140.29,139.81,130.94,130.24,129.66,128.88,127.40,126.54,126.12,126.02,125.72,125.45,125.07,122.93,122.73,44.72,41.44,38.36,37.83,29.99,21.65,21.18。

2- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol

To a solution of 8.40g (75.0mmol) of 4-fluorophenol and 13.5g (75.0mmol) of 3, 5-dimethyladamantan-1-ol in 150mL of dichloromethane was added dropwise a solution of 4.90mL (75.0mmol) of methanesulfonic acid and 5mL of acetic acid in 100mL of dichloromethane at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours, then poured carefully into 300mL 5% NaHCO₃In (1). The resulting mixture was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified using a Kugelrohr apparatus (1 mbar, 70 ℃ C.)14.2g (68%) of the title product are obtained as a pale yellow oil.¹H NMR(CDCl₃,400MHz):δ6.93(dd,J＝3.1,11.2Hz,1H),6.73(ddd,J＝3.1,7.4,8.6Hz,1H),6.55(dd,J＝4.9,8.6Hz),4.62(s,1H),2.16(dt,J＝3.1,6.3Hz,1H),1.91(m,2H),1.64-1.74(m,4H),1.35-1.45(m,4H),1.20(br.s,2H),0.87(s,6H)。¹³C NMR(CDCl₃,100MHz):δ158.49(J_F＝236Hz),150.19(J_F＝2.0Hz),137.69(J_F＝5.9Hz),117.12(J_F＝8.1Hz),114.13(J_F＝24.0Hz),112.57(J_F＝22.9Hz),50.92,46.44,43.05,38.70,38.48,31.38,30.84,29.90。

2-bromo-6- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol

To a solution of 14.2g (51.7mmol) of 2- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol in 200mL of dichloromethane was added dropwise a solution of 2.67mL (51.7mmol) of bromine in 100mL of dichloromethane at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours, then poured carefully into 200mL of 5% NaHCO₃In (1). The resulting mixture was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na ₂SO₄Dried and then evaporated to dryness. 17.5g (96%) of a pale yellow solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.06(dd,J＝3.0,7.0Hz,1H),6.93(dd,J＝2.9,10.8Hz,1H),5.59(s,1H),2.16(m,1H),1.89(br.s,2H),1.63-1.73(m,4H),1.34-1.44(m,4H),1.19(br.s,2H),0.86(s,6H)。¹³C NMR(CDCl₃,100MHz):δ157.21(J_F＝241Hz),146.61(J_F＝2.8Hz),137.97(J_F＝6.1Hz),115.34(J_F＝25.8Hz),113.64(J_F＝23.6Hz),110.83(J_F＝10.9Hz),54.77,50.48,45.71,42.61,38.96,38.03,31.02,30.42,29.49。

1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3, 5-dimethyladamantane

To a solution of 17.5g (49.5mmol) 2-bromo-6- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol in 200mL anhydrous THF at room temperature was added 2.17g (54.4mmol, 60% wt in mineral oil) sodium hydride in portions. Thereafter, 4.53mL (60.0mmol) of MOMCl was added dropwise over 1 hour. The reaction mixture was heated at 60 ℃ for 24 hours and then poured into 300mL of cold water. The crude product was extracted with 3X 200mL of dichloromethane. The combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. 19.6g (quantitative) of a white solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.13(dd,J＝3.1,6.8Hz,1H),6.98(dd,J＝3.1,10.9Hz,1H),5.19(s,2H),3.68(s,3H),2.16(m,1H),1.89(br.s,2H),1.64-1.74(m,4H),1.34-1.44(m,4H),1.19(br.s,2H),0.87(s,6H)。¹³C NMR(CDCl₃,100MHz):δ159.47(J_F＝245Hz),150.08(J_F＝3.3Hz),146.34(J_F＝6.4Hz),118.13(J_F＝25.4Hz),117.65(J_F＝10.7Hz),114.01(J_F＝23.4Hz),99.95,57.89,50.69,47.13,42.84,39.78,39.55,31.50,30.84,29.94。

2- (3- (3, 5-dimethyladamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) benzo [ b ] thiophene

To a solution of 3.38g (25.2mmol) of benzo [ b ] at-10 deg.C]Thiophene in 200mL dry THF was added dropwise to 9.50mL (23.9mmol, 2.5M) nBuLi in hexane. The reaction mixture was stirred at 0 ℃ for 2 hours, then 3.30g (23.9mmol) of ZnCl were added₂. Next, the resulting solution was warmed to room temperature, followed by addition of 5.00g (12.6mmol) of 1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3, 5-dimethyladamantane and 643mg (1.26mmol) of Pd [ P ] ^tBu₃]₂. The resulting mixture was stirred at 60 ℃ overnight and then poured into 250mL of water. The crude product was extracted with 3X 150mL of dichloromethane. The combined organic extracts were washed with Na₂SO₄Drying and then evaporatingAnd drying. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate 10:1, vol). 4.52g (80%) of a pale yellow oil are obtained.¹H NMR(CDCl₃,400MHz):δ7.85(dd,J＝1.1,7.3Hz,1H),7.79(dd,J＝1.5,7.0Hz,1H),7.51(s,1H),7.35(qd,J＝5.7,7.2,7.2,7.2,2H),7.06(s,1H),7.04(m,1H),4.72(s,2H),3.45(s,3H),2.20(m,1H),1.98(br.s,2H),1.71-1.83(m,4H),1.37-1.47(m,4H),1.22(br.s,2H),0.90(s,6H)。¹³C NMR(CDCl₃,100MHz):δ159.72(J_F＝241Hz),150.30,150.28,145.71,140.51(J_F＝2.0Hz),140.29,139.92,129.86,129.78,124.51(J_F＝3.5Hz),123.64(J_F＝3.5Hz),122.15,115.46(J_F＝23.7Hz),114.68(J_F＝23.6Hz),99.29,57.73,50.84,47.25,42.97,39.59,39.47,31.54,30.92,30.03。

3-bromo-2- (3- (3, 5-dimethyladamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) benzo [ b ] thiophene

To 4.50g (10.0mmol) of 2- (3- (3, 5-dimethyladamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) benzo [ b ] at room temperature]To a solution of thiophene in 150mL of chloroform was added 1.82g (10.2mmol) of N-bromosuccinimide. The reaction mixture was stirred at this temperature for 12 hours and then poured into 100mL of water. The crude product was extracted with 3X 50mL of dichloromethane. The combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was recrystallized from 110mL of n-hexane. 4.88g (92%) of a beige solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.87(d,J＝7.4Hz,1H),7.83(d,J＝8.0Hz,1H),7.49(dt,J＝1.1,7.1Hz,1H),7.43(dt,J＝1.3,7.3Hz,1H),7.11(dd,J＝3.2,10.9Hz,1H),6.99(dd,J＝3.2,7.6Hz,1H),4.59(s,2H),3.31(s,3H),2.19(m,1H),1.98(br.s,2H),1.70-1.83(m,4H),1.36-1.46(m,4H),1.21(br.s,2H),0.89(s,6H)。¹³C NMR(CDCl₃,100MHz):δ159.24(J_F＝242Hz),151.76(J_F＝2.9Hz),145.29(J_F＝6.4Hz),138.60,138.01,135.93,127.35(J_F＝9.0Hz),125.76,125.22,123.64,122.29,116.40(J_F＝23.4Hz),115.67(J_F＝23.6Hz),108.29,99.65,57.51,50.86,47.09,42.98,39.41,39.36,31.51,30.92,29.99。

6,6' - (pyridine-2, 6-diylbis (benzo [ b ] thiophene-3, 2-diyl)) bis (2- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol)

4.00g (7.55mmol) of 3-bromo-2- (3- (3, 5-dimethyladamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) benzo [ b ] b at-80 deg.C ]Thiophene in 50mL dry THF solution was added dropwise 3.08mL (7.70mmol, 2.5M) nBuLi in hexane. The reaction mixture is stirred at this temperature for 30 minutes, then 1.02g (7.70mmol) ZnCl are added₂. The resulting mixture was warmed to room temperature, and then 0.86g (3.63mmol) of 2, 6-dibromopyridine and 194mg (0.38mmol) of Pd [ P ] were added successively^tBu₃]₂. The resulting mixture was stirred at 60 ℃ overnight, poured into 100mL of water, and the crude product was extracted with dichloromethane (3X 50 mL). The combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 2mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The resulting mixture was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate-triethylamine ═ 100:10:1, volume). This gave 1.80g (56%, rotamer mixture) of a pale yellow foam.¹H NMR(CDCl₃,400MHz):δ7.85-7.91(m,4H),7.71(t,J＝7.8Hz,1H),7.43(m,4H),7.27(m,2H),6.82-6.87(m,4H),0.91-2.15(m,26H),0.69-0.87(m,12H)。¹³C NMR(CDCl₃,100MHz):δ157.34,154.97,153.27,148.98,140.47(J_F＝5.9Hz),140.03,138.96,138.56,138.09,132.36,125.19,124.00,122.91,122.19,119.08,115.02(J_F＝11.0Hz),114.79(J_F＝10.7Hz),50.73,46.35,46.14,43.07,42.71,38.59,37.57,31.39,31.15,30.87,30.74,30.03,29.93。

Hafnium dimethyl [6,6' - (pyridine-2, 6-diyl bis (benzo [ b ] thiophene-3, 2-diyl)) bis (2- (3, 5-dimethyladamantan-1-yl) -4-fluorophenylate ] (Complex 25)

623mg (1.94mmol) of hafnium tetrachloride (1.94mmol) at room temperature<0.05% Zr) to a suspension in 70mL of anhydrous toluene 3.01mL (8.73mmol, 2.9M) of MeMgBr in ether were added in one portion. The resulting suspension was stirred for 1 minute, and 1.73g (1.94mmol) of 6,6' - (pyridine-2, 6-diylbis (benzo [ b ] b) was added dropwise over 1 minute]Thiophene-3, 2-diyl)) bis (2- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol) in 20mL of anhydrous toluene. The reaction mixture was stirred at room temperature overnight and then evaporated to near dryness. The resulting solid was extracted with 2 × 50mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The resulting solid was washed with 15mL of n-hexane and then dried under vacuum. 1.40g (66%) of a beige solid were obtained as hexane solvate. C₅₉H₅₉F₂HfNO₂S₂×0.5(C₆H₁₄) Analytical calculation of (a): c, 65.45; h, 5.85; n,1.23 Found C65.68; h6.07; and N1.14.¹H NMR(C₆D₆,400MHz):δ7.31(m,2H),7.23(dd,J＝3.3,11.1Hz,2H),7.09(dd,J＝3.2,7.7Hz,2H),7.04(m,4H),6.83(m,2H),6.74(t,J＝7.8Hz,1H),6.35(d,J＝7.8Hz,2H),2.33(d,J＝12.1Hz,2H),2.05(d,J＝11.7Hz,2H),1.66(br.s,2H),1.03–1.50(m,20H),0.83(s,6H),0.76(s,6H),-0.10(s,6H)。¹³C NMR(CD₂Cl₂,100MHz):δ158.62,156.35(J_F＝234Hz),154.17,147.34(J_F＝1.8Hz),141.61,141.52(J_F＝6.1Hz),141.02,139.98,127.11,126.43,126.18,126.01,124.23(J_F＝8.8Hz),122.81,115.91(J_F＝16.8Hz),115.68(J_F＝16.8Hz),52.36,51.64,48.47,45.29,43.61,42.34,39.67,37.98,31.91,31.44,31.38,30.79,29.98,27.47。

2, 6-bis (2-bromophenyl) pyridine

2, 6-dibromopyridine (3.73g, 15.7mmol), 2-bromophenylboronic acid (6.26g, 31.4mmol), sodium carbonate (8.33g, 78.6mmol) and bis (bromoxynil) were added

Alkane (66mL) and water (33mL) were combined in a round bottom flask. The mixture was bubbled with nitrogen for 1 hour, then Pd (PPh) was added rapidly ₃)₄(1.82g, 1.57 mmol). The mixture was bubbled for 30 minutes and then heated to 100 ℃ overnight. The next day, the mixture was poured into water (200mL) and extracted with dichloromethane (4X 60 mL). The combined organics were dried over brine and then Na₂SO₄And (5) drying. Evaporation gave the crude product as a yellow-orange oily solid which was purified by crystallization from hot toluene. Yield 3.42g, 55.9%.

2- (3- (2, 3-dimethylbutan-2-yl) -2- (methoxymethyloxy) -5-methylphenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane

Tetrahydrofuran (20mL) was added to 1-bromo-3- (2, 3-dimethylbutan-2-yl) -2- (methoxymethoxy) -5-methylbenzene (2.89g, 9.17mmol) to form a light brown solution. A solution of BuLi (6.30mL, 10.1mmol) in hexane was added dropwise over 5 minutes at-50 ℃ to form a brown suspension. The mixture was stirred for 45 minutes, then 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolane (2.22g, 11.9mmol) was added to form a clear brown solution. The mixture was allowed to warm slowly to ambient temperature. After stirring overnight, the mixture was poured into water (100mL) and shaken. The mixture was extracted with dichloromethane (5X 50 mL). The combined organics were washed with water, brine, and then dried over MgSO 4. Volatiles were removed to give the product as a brown oil. Yield: 2.45g, 73.7%.

2', 2' - (pyridine-2, 6-diyl) bis (3- (2, 3-dimethylbutan-2-yl) -5-methyl- [1,1' -biphenyl ] -2-ol)

A100 mL round bottom flask was charged with 1-bromo-3- (2, 3-dimethylbutan-2-yl) -2- (methoxymethoxy) -5-methylbenzene (2.45g, 6.76mmol), 2, 6-bis (2-bromophenyl) pyridine (1.32g, 3.38mmol), Na₂CO₃(1.79g, 16.9mmol), bis

Alkane (20mL) and water (10 mL). The mixture was bubbled with nitrogen for 30 minutes, then solid Pd (PPh) was added₃)₄(0.391g, 0.340 mmol). The mixture was bubbled for an additional 15 minutes, then stirred and heated in an oil bath maintained at 100 ℃. After 17 hours, the brown mixture was combined with water (100mL) in a separatory funnel. Subjecting the mixture to CH₂Cl₂(6X 25 mL). The combined organics were dried over brine and then MgSO₄And (5) drying. Volatiles were removed to give 3.1g of a brown oil, which was combined with tetrahydrofuran (20mL), methanol (20mL) and concentrated HCl (1.0 mL). The mixture was stirred and heated to 60 ℃ for 4 hours. The volatiles were then evaporated and the residue was taken up in CH₂Cl₂Extract (100mL), wash with water (3X 50mL), and dry with brine (20 mL). The mixture was stirred over MgSO₄Dried, filtered and evaporated to give the crude product which is purified by silica gel column chromatography eluting with 2-8% ethyl acetate in hexane. Yield: 0.87g and 42 percent.

Dibenzylzirconium [2', 2' - (pyridine-2, 6-diyl) bis (3- (2, 3-dimethylbut-2-yl) -5-methyl- [1,1' -biphenyl ] -2-phenate) ] (Complex 29)

Toluene (5mL) was added to 2', 2' - (pyridine-2, 6-diyl) bis (3- (2, 3-dimethylbutan-2-yl) -5-methyl- [1,1' -biphenyl ] -2-ol) (0.260g, 0.425mmol) and tetrabenzyl zirconium (0.194g, 0.425mmol) to form a slightly cloudy orange solution. After stirring overnight, the mixture was evaporated and the residue was extracted with methylcyclohexane (5 mL). The cloudy orange solution was filtered and evaporated to a residue and pentane (4mL) was added. The mixture was milled to form a separate yellow-orange solid. The mixture was cooled to-15 ℃ for 1 hour, and then the solids were collected on a sintered dish. The solid was washed with cold pentane (2X 5mL) and dried under reduced pressure. The product was co-crystallized with 1 equivalent of hexane. Yield: 0.233g, 56.5%.

Hafnium dibenzyl [2', 2' - (pyridine-2, 6-diyl) bis (3- (2, 3-dimethylbut-2-yl) -5-methyl- [1,1' -biphenyl ] -2-phenate) ] (complex 30)

Toluene (5mL) was added to 2', 2' - (pyridine-2, 6-diyl) bis (3- (2, 3-dimethylbutan-2-yl) -5-methyl- [1,1' -biphenyl ] -2-ol) (0.208g, 0.340mmol) and hafnium tetrabenzyl (0.185g, 0.340mmol) to form a clear yellow-orange solution. The mixture was stirred overnight. The mixture was filtered and evaporated to a residue. Pentane (3mL) was added and the mixture was triturated until a dispersed solid formed. The mixture was cooled to-15 ℃ for 1 hour. The yellow solid was then collected on a fritted disc, washed with cold pentane (2 × 5mL) and dried under reduced pressure. The product was co-crystallized with 1 equivalent of hexane. Yield: 0.160g, 44.5%.

2- (adamantan-1-yl) -6-bromo-4-methylphenol

To a solution of 21.2g (87.0mmol) of 2- (adamantan-1-yl) -4-methylphenol in 200mL of dichloromethane was added dropwise a solution of 4.50mL (87.0mmol) of bromine in 100mL of dichloromethane at room temperature for 10 minutes. The resulting mixture was diluted with 400mL of water. The crude product was extracted with dichloromethane (3X 70mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried and then evaporated to dryness. 21.5g (77%) of a white solid are obtained.¹H 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),¹³C 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.

(1- (3-bromo-5-methyl-2- (methoxymethoxy) phenyl) adamantane

To a solution of 21.3g (66.4mmol) of 2- (adamantan-1-yl) -6-bromo-4-methylphenol in 400mL of THF at room temperature was added 2.79g (69.7mmol, 60% wt., in mineral oil) of sodium hydride in portions. To the resulting suspension was added dropwise 5.55mL (73.0mmol) of methoxymethyl chloride at room temperature over 10 minutes. The resulting mixture was stirred overnight and then poured into 200mL of water. The mixture thus obtained was extracted with dichloromethane (3X 200mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried and then evaporated to dryness. 24.3g (quantitative) of a white solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.24(d,J＝1.5Hz,1H),7.05(d,J＝1.8Hz,1H),5.22(s,2H),3.71(s,3H),2.27(s,3H),2.05-2.12(m,9H),1.78(m,6H)。¹³C 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。

2- (3-adamantan-1-yl) -5-methyl-2- (methoxymethoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane

To a solution of 20.0g (55.0mmol) (1- (3-bromo-5-methyl-2- (methoxymethoxy) phenyl) adamantane in 400mL anhydrous THF was added 22.5mL (56.4mmol) of 2.5M nBuLi in hexane dropwise at-80 deg.C for 20 min, the reaction mixture was stirred at that temperature for 1 h, then 16.7mL (82.2mmol) of 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolane was added, the resulting suspension was stirred at room temperature for 1 h, then poured into 300mL of water, the crude product was extracted with dichloromethane (3X 300mL), the combined organic extracts were extracted over Na₂SO₄Dried and then evaporated to dryness. 22.4g (99%) of a colorless paste are obtainedAnd (4) a natural oil.¹H 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)。¹³C 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。

1- (2 '-bromo-5-methyl-2- (methoxymethoxy) - [1,1' -biphenyl ] -3-yl) adamantane

To a solution of 10.0g (24.3mmol) of 2- (3-adamantan-1-yl) -5-methyl-2- (methoxymethoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 100mL of 1, 4-bis

To the solution in the alkane were added 7.22g (25.5mmol) of 2-bromoiodobenzene, 8.38g (60.6mmol) of potassium carbonate and 50mL of water in this order. The resulting mixture was purged with argon for 10 minutes, then 1.40g (1.21mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 150mL) and the combined organic extracts were washed with Na ₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-dichloromethane ═ 10:1 by volume). 10.7g (quantitative) of a white solid are obtained.¹H 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)。¹³C 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。

2- (3'- (adamantan-1-yl) -5' -methyl-2 '- (methoxymethyloxy) - [1,1' -biphenyl ] -2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane

To a solution of 10.7g (24.3mmol) of 1- (2 '-bromo-5-methyl-2- (methoxymethyloxy) - [1,1' -biphenyl at-80 deg.C]-3-yl) adamantane to a solution in 250mL anhydrous THF was added dropwise 11.6mL (29.1mmol) of a 2.5M solution of nBuLi in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 8.43mL (41.3mmol) 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 and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 300mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-ether ═ 10:1, volume). 8.60g (72%) of a colorless glassy solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.75(d,J＝7.4Hz,1H),7.33-7.44(m,2H),7.29-7.33(m,1H),7.07(br.s,1H),6.84(br.s,1H),4.50(d,J＝4.4Hz,1H),4.40(d,J＝4.4Hz,1H),3.27(s,3H),2.30(s,3H),2.21(br.s,6H),2.11(m,3H),1.80(m,6H),1.21(s,6H),1.15(s,6H)。¹³C NMR(CDCl₃,100MHz):δ151.52,145.68,142.04,136.74,134.30,131.47,130.51,130.23,129.79,126.69,126.06,98.73,83.39,57.22,41.47,37.20,37.04,29.19,25.00,24.16,20.97。

2', 2' - (pyridin-2, 6-diyl) bis (3-adamantan-1-yl) -5-methyl- [1,1' -biphenyl ] -2-ol)

To 4.00g (8.19mmol) of 2- (3'- (adamantan-1-yl) -5' -methyl-2 '- (methoxymethyloxy) - [1,1' -biphenyl]-2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 40mL of 1, 4-bis

To a solution in an alkane, 969mg (4.09 mg) was subsequently addedmmol) of 2, 6-dibromopyridine, 6.68g (20.5mmol) of cesium carbonate and 20mL of water. The resulting mixture was purged with argon for 10 minutes, and then 470mg (0.41mmol) of Pd (PPh3)4 was added. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3X 50mL) and the combined organic extracts were taken up in Na₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried 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, vol). The glassy solid obtained was triturated with 30mL of n-pentane and the precipitate thus obtained was filtered off (G3), washed with 2 × 10mL of n-pentane and dried in vacuo. 2.10g (72%) of a mixture of the two isomers are obtained as a white powder. ¹H NMR(CDCl₃,400MHz):δ7.64(s,1H),7.41-7.59(m,7H),7.33–7.38(m,2H),7.27(br.s,1H),7.02(d,J＝7.9Hz,1H),7.00(d,J＝7.8Hz,1H),6.87-6.92(m,3H),6.21(d,J＝1.7Hz,1H),2.26(s,3H),1.55-1.98(m,33H)。¹³C NMR(CDCl₃,100MHz)δ157.91,157.89,150.24,149.65,139.70,138.49,137.93,137.58,137.54,137.44,137.06,136.80,132.39,131.36,130.48,130.34,130.17,129.97,129.36,129.09,128.90,128.82,128.70,128.45,127.78,127.71,126.90,126.54,122.30,122.02,40.35,40.17,37.00,36.78,36.66,36.46,29.09,28.96,20.85,20.52。

(3r,5r,7r) -1- (2' -bromo-2- (methoxymethyloxy) -4', 5-dimethyl- [1,1' -biphenyl ] -3-yl) adamantane

To a solution of 6.11g (14.8mmol) of 2- (3-adamantan-1-yl) -5-methyl-2- (methoxymethoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 100mL of 1, 4-bis

To the solution in alkane, 4.62g (15.6mmol) of 2-bromo-4-methyliodobenzene, 5.12g (37.0mmol) of potassium carbonate and 50mL of water were then added. The resulting mixture was purged with argon for 10 minutes, then 850mg (0.741mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 150mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-dichloromethane ═ 10:1 by volume). 4.88g (73%) of a white solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.53(s,1H),7.27(d,J＝7.8Hz,1H),7.16–7.19(m,2H),6.90(d,J＝1.7Hz,1H),4.40(m,2H),3.27(s,3H),2.40(s,3H),2.35(s,3H),2.20(m,6H),2.12(m,3H),1.81(m,6H)。¹³C NMR(CDCl₃,100MHz):δ151.72,142.67,138.73,138.09,134.43,133.20,132.02,131.82,130.08,127.94,127.61,123.70,98.79,57.06,41.21,37.19,36.98,29.11,21.03,20.75。

2- (3'- ((3r,5r,7r) -adamantan-1-yl) -2' - (methoxymethyloxy) -4, 5 '-dimethyl- [1,1' -biphenyl ] -2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan

4.88g (10.7mmol) of (3r,5r,7r) -1- (2' -bromo-2- (methoxymethyloxy) -4', 5-dimethyl- [1,1' -biphenyl at-80 deg.C ]-3-yl) adamantane to a solution in 120mL of anhydrous THF was added dropwise 5.20mL (12.8mmol) of a 2.5M solution of nBuLi in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 4.43mL (21.4mmol) 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 and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 300mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-ether ═ 10:1, volume). 3.04g (57%) of a colorless glassy solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.53(s,1H),7.19-7.23(m,2H),7.02(d,J＝2.1Hz,1H),6.79(d,J＝1.7Hz,1H),4.43(m,2H),3.27(s,3H),2.37(s,3H),2.26(s,3H),2.17(m,6H),2.08(m,6H),1.77(m,6H),1.18(s,6H),1.13(s,6H)。¹³C NMR(CDCl₃,100MHz):δ151.71,142.84,141.95,136.61,135.53,134.91,131.41,130.65,130.63,130.21,126.52,98.73,83.38,57.28,41.49,37.20,37.07,29.22,25.02,24.20,21.03,20.99。

2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl ] -2-ol)

To a solution of 3.04g (6.05mmol) of 2- (3'- ((3r,5r,7r) -adamantan-1-yl) -2' - (methoxymethyloxy) -4, 5 '-dimethyl- [1,1' -biphenyl]-2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 40mL 1, 4-bis

To the solution in the alkane were then added 716mg (3.02mmol) of 2, 6-dibromopyridine, 4.92g (15.1mmol) of cesium carbonate and 20mL of water. The resulting mixture was purged with argon for 10 minutes, and then 350mg (0.30mmol) of Pd (PPh) was added ₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3X 50mL) and the combined organic extracts were taken up in Na₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried and then evaporated to dryness. Passing the residue through a flashChromatography was performed on silica gel 60(40-63 μm, eluent: hexane-ethyl acetate 10:1, vol). 0.74g (33%) of a mixture of the two isomers are obtained as a white foam.¹H NMR(CDCl₃,400MHz):δ7.66(s,1H),7.39-7.42(m,3H),7.22-7.35(m,5H),6.96-7.01(m,2H),6.85-6.91(m,3H),6.16(d,J＝1.5Hz,1H),2.49(s,3H),2.47(s,3H),2.26(s,3H),1.58-2.04(m,33H)。¹³C NMR(CDCl₃,100MHz)δ158.05,157.98,150.39,149.80,139.62,138.29,137.77,137.61,137.55,136.94,136.62,134.64,134.44,132.31,131.18,130.90,130.77,130.39,130.15,129.95,129.55,129.13,128.99,128.62,128.34,126.74,126.34,122.22,121.95,40.35,40.21,37.07,36.88,36.65,36.46,29.15,29.04,21.09,21.06,20.86,20.51。

(3r,5r,7r) -1- (2' -bromo-4 ' - (tert-butyl) -2- (methoxymethyloxy) -5-methyl- [1,1' -biphenyl ] -3-yl) adamantane

To a solution of 8.00g (19.4mmol) of 2- (3-adamantan-1-yl) -5-methyl-2- (methoxymethoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 50mL of 1, 4-bis

To the solution in the alkane were added 7.22g (21.3mmol) of 2-bromo-4- (tert-butyl) iodobenzene, 6.70g (48.5mmol) of potassium carbonate and 25mL of water in this order. The resulting mixture was purged with argon for 10 minutes, and then 2.20g (1.90mmol) of Pd (PPh) was added ₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 150mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-dichloromethane ═ 10:1 by volume). 5.20g (54%) of a white solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.68(s,1H),7.30-7.38(m,2H),7.16(s,1H),6.92(s,1H),4.49(m,2H),3.18(s,3H),2.35(s,3H),2.19(m,6H),2.12(m,3H),1.81(m,6H),1.37(s,9H)。¹³C NMR(CDCl₃,100MHz):δ152.30,151.61,142.80,138.05,134.67,132.11,131.74,130.01,129.70,127.66,124.22,123.89,98.83,56.93,41.29,37.24,37.00,34.60,31.22,29.14,21.05。

2- (3'- ((3r,5r,7r) -adamantan-1-yl) -4- (tert-butyl) -2' - (methoxymethyloxy) -5 '-methyl- [1,1' -biphenyl ] -2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan

To a solution of 5.12g (10.3mmol) of (3r,5r,7r) -1- (2' -bromo-4 ' - (tert-butyl) -2- (methoxymethoxy) -5-methyl- [1,1' -biphenyl at-80 deg.C]-3-yl) adamantane to a solution in 120mL of anhydrous THF was added dropwise 6.20mL (15.4mmol) of a 2.5M solution of nBuLi in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 5.23mL (25.6mmol) 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 and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 300mL) and the combined organic extracts were washed with Na ₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-ether ═ 10:1, volume). 3.30g (59%) of a colorless glassy solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.72(d,J＝2.1Hz,1H),7.44(dd,J＝8.1,2.2Hz,1H),7.29(d,J＝8.1Hz,1H),7.05(d,J＝2.0Hz,1H),6.83(d,J＝1.7Hz,1H),4.45(m,2H),3.24(s,3H),2.28(s,3H),2.20(m,6H),2.10(m,3H),1.79(m,6H),1.37(s,9H),1.20(br.s,6H),1.14(br.s,6H)。¹³C NMR(CDCl₃,100MHz):δ151.61,148.72,142.79,141.98,136.75,131.35,130.67,130.64,129.95,126.89,126.48,98.70，83.33，57.20，41.51，37.22，37.08，34.45，31.41，29.22，25.03，24.22，20.96。

2 ', 2' - (pyridine-2, 6-diyl) bis (3- ((3r, 5r, 7r) -adamantan-1-yl) -4 '- (tert-butyl) -5-methyl- [1, 1' -biphenyl ] -2-ol)

To a solution of 1.75g (3.21mmol) of 2- (3 '- ((3r, 5r, 7r) -adamantan-1-yl) -4- (tert-butyl) -2' - (methoxymethoxy) -5 '-methyl- [1, 1' -biphenyl]-2-yl) -4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolane in 40mL of 1, 4-bis

To the solution in the alkane, 381mg (1.61mmol) of 2, 6-dibromopyridine, 2.62g (8.03mmol) of cesium carbonate and 20mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, and then 180mg (0.16mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3X 50mL) and the combined organic extracts were taken up in Na₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70mL) and the combined organic extracts were extracted with 5% NaHCO ₃Washing in Na₂SO₄Dried 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, vol). 0.60g (45%) of a mixture of the two isomers was obtained as a white foam.¹H NMR(CDCl₃400 MHz): δ 7.72 and 7.08(2s, 2H), 7.40-7.53(m, 5H), 7.21-7.26(m, 2H), 6.94-7.00(m, 2H), 6.80-6.86 and 6.09(2m, 4H), 1.53-1.95(m, 30H), 1.39 and 1.40(2s, 18H).¹³C NMR(CDC1₃，100MHz)δ158.53，150.71，150.54，149.85，139.47，137.94，137.52，136.66，134.45，132.05，130.80，130.68，129.49，129.04，128.58，128.41，127.40，127.24，126.78，126.36，125.72，122.26，122.02，40.38，40.28，37.05，36.87，36.70，36.52，34.67，31.58,31.39,29.11,28.98,20.87,20.52。

2', 2' - (4-methoxypyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -4'- (tert-butyl) -5-methyl- [1,1' -biphenyl ] -2-ol)

To a solution of 1.50g (2.75mmol) of 2- (3'- ((3r,5r,7r) -adamantan-1-yl) -4- (tert-butyl) -2' - (methoxymethoxy) -5 '-methyl- [1,1' -biphenyl]-2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 40mL of 1, 4-bis

To the solution in alkane, 367mg (1.38mmol) of 2, 6-dibromo-4-methoxypyridine, 2.25g (6.90mmol) of cesium carbonate and 20mL of water were then added. The resulting mixture was purged with argon for 10 minutes, and then 160mg (0.138mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3X 50mL) and the combined organic extracts were taken up in Na ₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried 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, vol). 1.04g (89%) of a mixture of the two isomers are obtained as a white foam.¹H NMR(CDCl₃400MHz delta 7.88 and 7.31(2s,2H),7.46-7.57(m,4H),7.21-7.27(m,2H),6.83(m,2H),6.46-6.48(m,2H),6.12 and 6.88(2m,2H),3.50 and 3.41(2s,3H),1.57-1.95(m,30H),1.40 and 1.41(2s, 18H).¹³C NMR(CDCl₃,100MHz)δ160.07,150.75,150.50,139.59,137.92,134.48,131.99,130.84,130.77,129.49,129.11,128.53,127.13,126.42,125.79,108.64,108.33,55.22,40.54,40.29,37.08,36.92,36.77,34.69,31.46,31.42,29.17,29.06,20.57。

2- (adamantan-1-yl) -6-bromo-4- (tert-butyl) phenol

To a solution of 236g (830mmol) of 2- (adamantan-1-yl) -4- (tert-butyl) phenol in 2000mL of dichloromethane was added dropwise a solution of 132g (830mmol) of bromine in 400mL of dichloromethane for 1 hour at room temperature. The resulting mixture was diluted with 2,000mL of water. The resulting mixture was extracted with dichloromethane (3X 500mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried and then evaporated to dryness. 299g (99%) of a white solid are obtained. ¹H NMR(CDCl₃,400MHz):δ7.32(d,J＝2.3Hz,1H),7.19(d,J＝2.3Hz,1H),5.65(s,1H),2.18-2.03(m,9H),1.78(m,6H),1.29(s,9H)。¹³C NMR(CDCl₃,100MHz):δ148.07,143.75,137.00,126.04,123.62,112.11,40.24,37.67,37.01,34.46,31.47,29.03。

(1- (3-bromo-5- (tert-butyl) -2- (methoxymethoxy) phenyl) adamantane

To a solution of 330g (910mmol)2- (adamantan-1-yl) -6-bromo-4- (tert-butyl) phenol in 3,000mL THF was added 40.0g (1.00mol, 60% wt in mineral oil) of sodium hydride portionwise at room temperature. 76.0mL (1.00mol) of methoxymethyl chloride was added dropwise to the resulting suspension at room temperature over 40 minutes. The resulting mixture was stirred overnight and then poured into 2,000ml of water. The desired product was extracted with dichloromethane (3X 900mL) and 5% NaHCO₃The combined organic extracts were washed over Na₂SO₄Dried and then evaporated to dryness. 367g (99%) of a white solid were obtained.¹H NMR(CDCl₃,400MHz):δ7.39(d,J＝2.4Hz,1H),7.27(d,J＝2.4Hz,1H),5.23(s,2H),3.71(s,3H),2.20-2.04(m,9H),1.82-1.74(m,6H),1.29(s,9H)。¹³C NMR(CDCl₃,100MHz):δ150.88,147.47,144.42,128.46,123.72,117.46,99.53,57.74,41.31,38.05,36.85,34.58,31.30,29.08。

2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane

To a solution of 183.5g (450mmol) (1- (3-bromo-5- (tert-butyl) -2- (methoxymethoxy) phenyl) adamantane in 2,500mL anhydrous THF was added 190mL (473mmol) of 2.5M nBuLi in hexane dropwise at-80 deg.C for 20 min the reaction mixture was stirred at this temperature for 1 h, then 120mL (585mmol) of 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolane was added, the resulting suspension was stirred at room temperature for 1 h, then poured into 300mL water, the resulting mixture was evaporated to about 1L, the crude extracted with dichloromethane (3X 800mL), the combined organic extracts were extracted over Na ₂SO₄Dried and then evaporated to dryness. 204.7g (quantitative) of a colorless solid were obtained.¹H NMR(CDCl₃,400MHz):δ7.54(d,J＝2.5Hz,1H),7.43(d,J＝2.6Hz,1H),5.18(s,2H),3.60(s,3H),2.24-2.13(m,6H),2.09(br.s.,3H),1.85-1.75(m,6H),1.37(s,12H),1.33(s,9H)。¹³C NMR(CDCl₃,100MHz):δ159.64,144.48,140.55,130.58,127.47,100.81,83.48,57.63,41.24,37.29,37.05,34.40,31.50,29.16,24.79。

In a 2L pressure vessel, 150g (330mmol)2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane, 1000mL of di

Alkane, 93.4g (330mmol) 2-bromoiodobenzene, 114g (825mmol) potassium carbonate and 500mL water. The resulting mixture was purged with argon for 10 minutes, and then 19.1g (17.0mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 115 ℃ for 12 hours, then cooled to room temperature and diluted with 500mL of water. The crude product was extracted with dichloromethane (3X 700mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-dichloromethane ═ 10:1 by volume). 112g (70%) of a white solid are produced.¹H NMR(CDCl₃,400MHz):δ7.68(dd,J＝1.0,8.0Hz,1H),7.42(dd,J＝1.7,7.6Hz,1H),7.37-7.32(m,2H),7.20(dt,J＝1.8,7.7Hz,1H),7.08(d,J＝2.5Hz,1H),4.53(d,J＝4.6Hz,1H),4.40(d,J＝4.6Hz,1H),3.20(s,3H),2.23-2.14(m,6H),2.10(br.s.,3H),1.86-1.70(m,6H),1.33(s,9H)。¹³C NMR(CDCl₃,100MHz):δ151.28,145.09,142.09,141.47,133.90,132.93,132.41,128.55,127.06,126.81,124.18,123.87,98.83,57.07,41.31,37.55,37.01,34.60,31.49,29.17。

To 223g (462mmol) of 1- (2 '-bromo-5- (tert-butyl) -2- (methoxymethoxy) - [1,1' -biphenyl at-80 deg.C ]-3-yl) adamantane to a solution of 3,000mL dry THF was added 194mL (485mmol) of a 2.5M solution of nBuLi in hexane dropwise over 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 122mL (600mmol) of 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolane were added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300ml of water. The resulting mixture was evaporated to about 1 l, the crude product was extracted with dichloromethane (3X 300mL), and the combined organic extracts were washed with Na₂SO₄Drying, then evaporating to dryness. 240.9g (quantitative) of a white solid are produced.¹H NMR(CDCl₃,400MHz):δ7.75(d,J＝7.3Hz,1H),7.44-7.36(m,1H),7.36-7.30(m,2H),7.30-7.26(m,1H),6.96(d,J＝2.4Hz,1H),4.53(d,J＝4.7Hz,1H),4.37(d,J＝4.7Hz,1H),3.22(s,3H),2.26-2.14(m,6H),2.09(br.s.,3H),1.85-1.71(m,6H),1.30(s,9H),1.15(s,6H),1.10(s,6H)。¹³C NMR(CDCl₃,100MHz):δ151.35,146.48,144.32,141.26,136.15,134.38,130.44,129.78,126.75,126.04,123.13,98.60,83.32,57.08,41.50,37.51,37.09,34.49,31.57,29.26,24.92,24.21。

2', 2' - (4-methoxypyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-ol)

To a solution of 2.00g (3.77mmol) of 2- (3'- (adamantan-1-yl) -5' - (tert-butyl) -2'- (methoxymethoxy) - [1,1' -biphenyl]-2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 40mL of bis

To the solution in alkane, 503mg (1.88mmol) of 2, 6-dibromo-4-methoxypyridine, 3.07g (9.42mmol) of cesium carbonate and 20mL of water were then added. The resulting mixture was purged with argon for 10 minutes, then 440mg (0.380mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12h, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3X 50mL) and the combined organic extracts were extracted over Na ₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried 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, vol). Product produced by birth1.33g (86%) of a mixture of the two isomers were produced as a white foam.¹H NMR(CDCl₃400 MHz). delta.8.31 and 7.13(2s,2H),7.37-7.60(m,8H),7.09-7.11(m,2H),6.55 and 6.98(2m,2H),6.50 and 6.42(2s,2H),3.37 and +3.36(2s,3H),1.87-2.00(m,18H),1.60-1.69(m,12H),1.21 and 1.00(2s, 18H).¹³C NMR(CDCl₃,100MHz)δ165.87,159.18,149.98,141.89,139.42,137.80,137.42,131.50,130.81,129.86,129.05,127.75,126.53,122.80,108.97,55.12,40.57,40.32,37.07,37.01,34.02,31.58,31.46,29.11,29.02。

2', 2' - (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-ol)

To the solution in alkane, 406mg (1.88mmol) of 2, 6-dichloro-4-trifluoromethylpyridine, 3.07g (9.42mmol) of cesium carbonate and 20ml of water were then added. The resulting mixture was purged with argon for 10 minutes, then 440mg (0.380mmol) of Pd (PPh) was added ₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3X 50mL) and the combined organic extracts were taken up in Na₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried 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, vol). Generation of 131g (83%) of a mixture of the two isomers as a white foam.¹H NMR(CDCl₃,400MHz):δ7.40-7.55(m,8H),7.04-7.14+5.62(2m,6H),6.86+6.56(2d,J＝2.4Hz,2H),1.90-2.02(m,18H),1.60-1.74(m,12H),1.16+1.01(2s,18H)。¹³C NMR(CDCl₃,100MHz)δ159.29,159.09,149.57,148.84,142.43,142.33,139.45,138.78,138.45,137.60,137.22,136.72,136.24,131.62,131.51,130.76,130.52,129.76,129.71,128.53,128.39,128.16,127.42,126.03,125.28,123.46,123.34,118.20(q,Jc,_F＝3.5Hz),40.45,40.34,37.07,37.03,34.21,34.06,31.45,31.42,29.11,29.06。

(3r,5r,7r) -1- (2' -bromo-5- (tert-butyl) -2- (methoxymethyloxy) -4' -methyl- [1,1' -biphenyl ] -3-yl) adamantane

To a solution of 10.0g (22.0mmol) of 2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 100mL of 1, 4-dioxaborolane

To the solution in alkane, 6.83g (23.0mmol) of 2-bromo-4-methyliodobenzene, 7.60g (55.0mmol) of potassium carbonate and 50mL of water were then added. The resulting mixture was purged with argon for 10 minutes, and then 1.27g (1.10mmol) of Pd (PPh) was added ₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 150mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-dichloromethane ═ 10:1 by volume). 8.77g (80%) of a white solid are produced.¹H NMR(CDCl₃,400MHz):δ7.56(m,1H),7.32-7.39(m,2H),7.19(d,J＝7.8Hz,1H),7.11(d,J＝2.5Hz,1H),4.59(m,1H),4.47(m,1H),3.29(s,3H),2.41(s,3H),2.25(m,6H),2.15(m,3H),1.84(m,6H),1.37(s,9H)。¹³C NMR(CDCl₃,100MHz):δ151.48,144.93,141.94,138.66,138.46,133.66,133.32,132.02,127.90,127.02,123.82,123.66,98.75,57.09,41.30,37.53,37.04,34.56,31.48,29.19,20.76.

4- ((3r,5r,7r) -adamantan-1-yl) -2- (tert-butyl) -6-isopropoxy-8-methyl-6H-dibenzo [ c, e ] [1,2] oxaborole

8.75g (17.6mmol) of (3r,5r,7r) -1- (2' -bromo-5- (tert-butyl) -2- (methoxymethoxy) -4' -methyl- [1,1' -biphenyl at-80 deg.C]-3-yl) adamantane to a solution in 120mL of anhydrous THF was added dropwise 8.44mL (21.1mmol) of a 2.5M solution of nBuLi in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 6.12mL (30.0mmol) 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 and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 300mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was recrystallized from 20mL of hot isopropanol and the crystalline material obtained was filtered off (G3), washed with 5mL of cold isopropanol and dried in vacuo. 4.90g (51%) white crystals were obtained. ¹H NMR(CDCl₃,400MHz):δ8.07(d,J＝8.3Hz,1H),8.03(d,J＝2.0Hz,1H),7.87(m,1H),7.46(d,J＝8.2Hz,1H),7.40(d,J＝2.0Hz,1H),5.25(sept,J＝6.1Hz,1H),2.46(s,3H),2.30(m,6H),2.16(m,3H),1.85(m,6H),1.42(s,9H),1.42(d,J＝6.0Hz,6H)。¹³C NMR(CDCl₃,100MHz):δ147.99,143.84,138.75,138.38,136.14,133.08,132.97,123.55,122.32,121.59,117.90,65.66,40.77,37.45,37.19,34.75,31.67,29.17,24.74,21.21。

2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-ol)

To a solution of 1.60g (3.62mmol) of 4- ((3r,5r,7r) -adamantan-1-yl) -2- (tert-butyl) -6-isopropoxy-8-methyl-6H-dibenzo [ c, e ]][1,2]1, 4-Di-Oxaborohexane solution at 40mL

To the solution in alkane, 429mg (1.81mmol) of 2, 6-dibromopyridine, 2.95g (9.10mmol) of cesium carbonate and 20mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, then 210mg (0.180mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The crude product was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried 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, vol). 1.11g (74%) of a mixture of the two isomers are obtained as a white foam.¹H NMR(CDCl₃,400MHz):δ8.15+6.81(2s,2H),7.31-7.40(m,3H),7.21-7.24(m,2H),6.90-7.03+6.49(2m,6H),2.42+2.41(2s,6H),1.73-2.06(m,18H),1.60-1.67(m,12H),1.13+0.97(2s,18H)。¹³C NMR(CDCl₃,100MHz)δ157.96,157.77,150.22,149.45,141.67,139.30,137.45,137.40,136.71,135.04,131.60,131.43,130.82,129.84,129.64,126.50,125.77,122.58,122.42,40.52,40.39,37.11,37.03,36.85,33.99,31.48,29.19,29.11,21.14。

2', 2' - (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-ol)

To a solution of 1.60g (3.62mmol)4- ((3r,5r,7r) -adamantan-1-yl) -2- (tert-butyl) -6-isopropoxy-8-methyl-6H-dibenzo [ c, e ] ][1,2]Oxaborohexane in 40mL of 1, 4-bis

To a solution in alkane, 391mg (1.81 mmo) of the solution was addedl)2, 6-dichloro-4-trifluoromethylpyridine, 2.95g (9.10mmol) cesium carbonate and 20mL water. The resulting mixture was purged with argon for 10 minutes, then 210mg (0.180mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The crude product was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried 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, vol). 1.01g (62%) of a mixture of the two isomers are obtained as a white foam.¹H NMR(CDCl₃400MHz delta 7.44 and 5.97(2s,2H),7.34-7.38(m,6H),7.12(d, J ═ 2.4Hz,2H),7.07(s,2H),6.92 and 6.56(2m,2H),2.49 and 2.48(2s,6H),1.85-2.04(m,18H),1.65-1.75(m,12H),1.18 and 1.03(s, 18H).¹³C NMR(CDCl₃,100MHz)δ159.41,159.19,149.81,149.80,149.05,142.20,142.16,139.08,138.70,138.57,138.37,138.10,138.01,137.26,136.25,134.77,134.03,131.51,131.27,130.91,130.49,130.41,128.66,127.64,126.17,125.43,123.69,123.31,123.12,118.23(q,Jc,_F＝3.8Hz),117.88(q,Jc,_F＝3.8Hz),40.47,40.34,37.08,37.06,34.02,31.42,29.17,29.08,26.91,21.14。

2', 2' - (4-methoxypyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-ol)

To a solution of 1.60g (3.62mmol)4- ((3r,5r,7r) -adamantan-1-yl) -2- (tert-butyl) -6-isopropoxy-8-methyl-6H-dibenzo [ c, e ]][1,2]Oxaborohexane in 40mL of 1, 4-bis

To the solution in alkane, 483mg (1.81mmol) of 2, 6-dibromo-4-methoxypyridine, 2.95g (9.10mmol) of cesium carbonate and 20mL of water were then added. The resulting mixture was purged with argon for 10 minutes, then 210mg (0.180mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The crude product was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried 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, vol). 910mg (58%) of a mixture of the two isomers are obtained as a white foam.¹H NMR(CDCl₃,400MHz):δ8.39+6.52(2s,2H),7.25-7.45(m,7H),7.00-7.12(m,2H),6.42-6.56(m,3H),3.41+3.38(2s,3H),2.47(s,6H),1.87-2.02(m,18H),1.62-1.75(m,12H),1.24+1.02(2s,18H)。¹³C NMR(CDCl₃,100MHz)δ165.79,159.28,159.22,150.13,149.66,141.90,141.78,139.28,138.72,137.54,137.36,136.77,134.89,134.80,132.26,131.39,131.37,130.94,130.08,129.87,129.75,129.34,126.60,125.60,123.01,122.58,108.92,108.34,55.09,54.73,40.61,40.35,37.08,37.07,36.87,34.22,33.99,31.56,31.46,29.19,29.07,26.90,22.65,21.15。

(3r,5r,7r) -1- (2' -bromo-5- (tert-butyl) -4' -isopropyl-2- (methoxymethoxy) - [1,1' -biphenyl ] -3-yl) adamantane

To the solution in alkane, 6.83g (23.0mmol) of 2-bromo-4-isopropyliodobenzene, 7.60g (55.0mmol) of potassium carbonate and 50mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, and then 1.27g (1.10mmol) of Pd (PPh) was added ₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 150mL) and the combined organic extracts were washed with Na₂SO₄Drying and then evaporating toAnd (5) drying. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-dichloromethane ═ 10:1 by volume). 11.5g (95%) of a white solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.53(d,J＝1.7Hz,1H),7.30-7.33(m,2H),7.19(dd,J＝8.0,1.7Hz,1H),7.08(d,J＝2.5Hz,1H),4.52(m,1H),4.39(m,1H),3.18(s,3H),2.92(sept,J＝6.9Hz,1H),2.14-2.20(m,6H),2.10(br.s,3H),1.74-1.84(m,6H),1.32(s,9H),1.28(d,J＝6.9Hz,6H)。¹³C NMR(CDCl₃,100MHz):δ151.35,149.85,145.03,142.04,138.73,133.91,132.21,130.79,126.96,125.33,124.02,123.71,98.76,57.03,41.35,37.57,37.04,33.63,31.50,29.20,24.83,23.90。

2- (3'- ((3r,5r,7r) -adamantan-1-yl) -5' - (tert-butyl) -4-isopropyl-2 '- (methoxymethyloxy) - [1,1' -biphenyl ] -2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan

To a solution of 11.3g (21.5mmol) of (3r,5r,7r) -1- (2' -bromo-5- (tert-butyl) -4' -isopropyl-2- (methoxymethoxy) - [1,1' -biphenyl at-80 deg.C]-3-yl) adamantane to a solution in 200mL anhydrous THF was added dropwise 9.00mL (22.6mmol) of a 2.5M solution of nBuLi in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 6.98mL (32.2mmol) 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 and then poured into 100mL of water. The resulting mixture was evaporated to about 150mL and the crude product was extracted with dichloromethane (3X 100 mL). The combined organic extracts were washed with Na ₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-ether ═ 10:1, volume). 6.80g (56%) of a white solid are produced.¹H NMR(CDCl₃,400MHz):δ7.57(s,1H),7.24-7.28(m,3H),6.97(d,J＝2.4Hz,1H),4.52(m,1H),4.37(m,1H),3.20(s,3H),2.95(sept,J＝6.9Hz,1H),2.17–2.21(m,6H),2.09(br.s,3H),1.73-1.84(m,6H),1.29(s,9H),1.28(d,J＝6.9Hz,6H),1.15(s,6H),1.10(s,6H)。¹³C NMR(CDCl₃,100MHz):δ151.43,146.50,144.22,143.92,141.17,136.17,132.40,130.45,127.73,126.84,122.94,98.52,83.26,57.06,41.50,37.49,37.10,34.48,33.86,31.58,29.26,24.94,24.41,24.13,24.07。

2', 2' - (pyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl ] -2-ol)

To a solution of 3.20g (5.66mmol) of 2- (3'- (adamantan-1-yl) -5' - (tert-butyl) -2'- (methoxymethoxy) - [1,1' -biphenyl]-2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 40mL of 1, 4-bis

To the solution in alkane, 609mg (2.83mmol) of 2, 6-dibromopyridine, 5.00g (14.2mmol) of cesium carbonate and 20mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, and then 300mg (0.260mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3X 50mL) and the combined organic extracts were taken up in Na₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70mL) and the combined organic extracts were extracted with 5% NaHCO ₃Washing in Na₂SO₄Dried 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, vol). 1.34g (54%) of a mixture of the two isomers are obtained as a white foam.¹H NMR(CDCl₃,400MHz):δ8.26+6.83(2s,2H),6.95-7.58+6.52(2m,13H),3.01(sept,J＝6.9Hz,2H),1.85-2.02(m,18H),1.62-1.68(m,12H),1.33(d,J＝6.9Hz,6H),1.32(d,J＝6.9Hz,6H),1.13+1.00(2s,18H)。¹³C NMR(CDCl₃,100MHz)δ158.28,157.98,150.28,149.48,148.14,148.02,141.61,141.46,139.28,137.50,136.74,136.20,135.43,135.13,132.10,131.67,130.07,129.29,128.97,128.07,127.18,126.90,126.58,125.77,122.74,122.50,122.44,122.20,40.51,40.30,37.08,37.05,36.81,34.17,34.00,33.84,33.78,31.50,31.40,29.15,29.10,24.14,23.81。

2', 2' - (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3r, 5r, 7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl ] -2-ol)

To a solution of 1.77g (3.09mmol) of 2- (3'- (adamantan-1-yl) -5' - (tert-butyl) -2'- (methoxymethoxy) - [1,1' -biphenyl]-2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 40mL of bis

To the solution in the alkane, 325mg (1.51mmol) of 2, 6-dichloro-4-trifluoromethylpyridine, 3.00g (9.04mmol) of cesium carbonate and 20mL of water were then added. The resulting mixture was purged with argon for 10 minutes, and then 200mg (0.190mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3X 50mL) and the combined organic extracts were taken up in Na₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70mL) and the combined organic extracts were extracted with 5% NaHCO ₃Washing in Na₂SO₄Dried 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, vol). 1.17g (82%) of a mixture of the two isomers were obtained as a white foam.¹H NMR(CDCl₃400 MHz). delta.7.35-7.46 and 5.99(2m,8H),7.06-7.13(m,4H),6.95 and 6.56(2m,2H),3.05(sept, J ═ 6.9Hz,2H),1.86-2.04(m,18H),1.63-1.71(m,12H),1.36(d, J ═ 6.9Hz,6H),1.34(d, J ═ 6.9Hz,6H),1.15 and 1.01(2s, 18H).¹³C NMR(CDCl₃,100MHz)δ159.68,149.86,149.11,148.81,142.12,138.59,137.29,136.18,135.10,131.67,131.57,128.98,128.81,127.66,126.29,125.43,123.10,118.27(q,J_C,F＝3.5Hz),40.48,40.28,37.06,36.87,34.02,33.84,31.43,31.39,29.12,29.07,24.07,23.86。

2', 2' - (4-methoxypyridine-2, 6-diyl) bis (3- ((3r, 5r, 7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl ] -2-ol)

To a solution of 1.77g (3.09mmol) of 2- (3 '- (adamantan-1-yl) -5' - (tert-butyl) -2 '- (methoxymethoxy) - [1,1' -biphenyl]-2-yl) -4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolane in 40mL of bis

To the solution in alkane, 400mg (1.51mmol) of 2, 6-dibromo-4-methoxypyridine, 3.00g (9.04mmol) of cesium carbonate and 20mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, and then 200mg (0.190mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3X 50mL) and the combined organic extracts were taken up in Na ₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried 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, vol). 1.01g (74%) of the two isomers are obtainedThe mixture was a white foam.¹H NMR(CDCl₃400 MHz): δ 8.40 and 7.02(2s, 2H), 7.23-7.44(m, 6H), 7.07(m, 2H), 6.56-6.58(m, 2H), 6.41(m, 2H), 3.50 and 3.37(2s, 3H), 3.02(sept, J ═ 6.9Hz, 2H), 1.85-2.02(m, 18H), 1.62-1.70(m, 12H), 1.34(d, J ═ 6.9Hz, 12H), 1.19+1.00(2s, 18H).¹³C NMR(CDCl₃，100MHz)δ165.74，159.62，150.20，148.30，141.73，139.35，137.37，135.18，131.38，129.99，129.03，127.34，127.03，126.71，125.71，122.56，108.94，55.12，40.61，37.08，37.06，34.01，33.76，31.48，29.13，24.12，23.83。

2- (adamantan-1-yl) -4-fluorophenol

To a solution of 30.0g (268mmol) of 4-fluorophenol and 40.8g (268mmol) of adamantane 1-ol in 300ml of dichloromethane are added dropwise a solution of 17.4ml (268mmol) of methanesulfonic acid and 20ml of acetic acid in 100ml of dichloromethane at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours, then poured carefully into 300mL of 5% NaHCO ₃In (1). The crude product was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified using a Kugelrohr apparatus (0.3 mbar, 95 ℃) to yield 49.3g (75%) of the title product as a pale yellow oil.¹H NMR(CDCl₃,400MHz):δ6.92(dd,J＝11.2,3.1Hz,1H),6.73(ddd,J＝8.7,7.4,3.1Hz,1H),6.60(dd,J＝8.7,5.0Hz,1H),4.34(br.s,1H),2.08-2.11(m,9H),1.75-1.80(m,9H),1.58-1.67(m,3H),¹³C NMR(CDCl₃,100MHz):δ158.28(d,J_C,F＝236Hz),150.60(d,J_C,F＝2.0Hz),138.27(d,J_C,F＝5.9Hz),117.07(d,J_C,F＝8.1Hz),113.88(d,J_C,F＝23.9Hz),112.36(d,J_C,F＝23.0Hz),45.05,40.13,36.88,35.90,30.65,28.88。

2-bromo-6- (adamantan-1-yl) -4-fluorophenol

To a solution of 49.3g (200mmol) of 2- (adamantan-1-yl) -4-fluorophenol in 500mL of dichloromethane was added dropwise a solution of 10.3mL (200mmol) of bromine in 100mL of dichloromethane at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours, then poured carefully into 200mL of 5% NaHCO₃In (1). The crude product was extracted with dichloromethane (3X 150mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. 65.0g (quantitative) of a pale yellow solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.07(dd,J＝7.0,3.0Hz,1H),6.92(dd,J＝10.8,3.0Hz,1H),5.60(s,1H),2.07(br.s,9H),1.77(br.s,6H)。¹³C NMR(CDCl₃,100MHz):δ157.21(d,J_C,F＝241Hz),147.03(d,J_C,F＝3.0Hz),138.91(d,J_C,F＝5.9Hz),115.66(d,J_C,F＝25.8Hz),113.97(d,J_C,F＝23.6Hz),111.21(d,J_C,F＝10.9Hz),39.88,37.60,36.82,28.86。

(3r,5r,7r) -1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) adamantane

To a solution of 48.4g (150mmol) 2-bromo-6- (adamantan-1-yl) -4-fluorophenol in 500mL anhydrous THF at room temperature was added 6.30g (155mmol, 60% wt. in mineral oil) sodium hydride in portions. Thereafter, 13.7mL (180mmol) of MOMCl were added dropwise over 1 hour. The reaction mixture was heated at 60 ℃ for 24 hours and then poured into 300mL of cold water. The crude product was extracted with 3X 200mL of dichloromethane. The combined organic extracts were washed with Na ₂SO₄Dried and then evaporated to dryness. 56.0g (quantitative) of a white solid was obtained.¹H NMR(CDCl₃,400MHz):δ7.12(dd,J＝6.9,3.1Hz,1H),6.98(dd,J＝10.9,3.1Hz,1H),5.20(s,2H),3.69(s,3H),2.07(br.s,9H),1.76(br.s,6H)。¹³C NMR(CDCl₃,100MHz):δ159.51(d,J_C,F＝245Hz),149.86(d,J_C,F＝3.3Hz),146.93(d,J_C,F＝6.5Hz),118.09(d,J_C,F＝25.4Hz),117.67(d,J_C,F＝10.5Hz),113.99(d,J_C,F＝23.6Hz),99.72,57.83,40.99,38.06,36.67,28.92。

2- ((3r,5r,7r) -3-adamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan

To a solution of 28.0g (75.8mmol) of (1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) adamantane in 400mL anhydrous THF at-80 deg.C was added dropwise 30.3mL (75.8mmol) of a 2.5M solution of nBuLi in hexane for 20 minutes the reaction mixture was stirred at that temperature for 1 hour, then 20.1mL (98.5mmol) 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 300mL of water the crude product was extracted with dichloromethane (3X 300mL), the combined organic extracts were extracted over Na₂SO₄Dried and then evaporated to dryness. The residue was recrystallized from isopropanol. 27.8g (88%) of a white solid were produced.¹H NMR(CDCl₃,400MHz):δ7.19(dd,J＝7.7,3.3Hz,1H),7.06(dd,J＝10.9,3.3Hz,1H),5.12(s,2H),3.57(s,3H),2.10(br.s,6H),2.06(br.s,3H),1.75(br.,s 6H),1.34(s,12H)。¹³C NMR(CDCl₃,100MHz):δ159.46(d,J_C,F＝241Hz),157.48(d,J_C,F＝2.0Hz),144.23(d,J_C,F＝5.7Hz),119.42(d,J_C,F＝21.0Hz),117.35(d,J_C,F＝24.0Hz),100.98,83.96,57.73,40.97,37.29,36.87,28.99,24.79。

(3r,5r,7r) -1- (2' -bromo-5-fluoro-4 ' -isopropyl-2- (methoxymethoxy) - [1,1' -biphenyl ] -3-yl) adamantane

To 8.00g (19.21mmol) of 2- ((3 r)5r,7r) -3-adamantan-1-yl) -5-fluoro-2- (methoxymethyloxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan in 60mL of 1, 4-bis

To the solution in alkane, 6.24g (19.2mmol) of 2-bromo-4-isopropyliodobenzene, 6.63g (48.0mmol) of potassium carbonate and 50mL of water were then added. The resulting mixture was purged with argon for 10 minutes, and then 1.10g (0.96mmol) of Pd (PPh) was added₃)₄. This mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 150mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-dichloromethane ═ 10:1 by volume). 4.70g (50%) of a white solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.53(d,J＝1.6Hz,1H),7.27(d,J＝7.9Hz,1H),7.20(dd,J＝7.9,1.6Hz,1H),7.03(dd,J＝11.0,3.2Hz,1H),6.79(dd,J＝7.9,3.2Hz,1H),4.48(m,1H),4.40(m,1H),3.16(s,3H),2.93(sept,J＝6.9Hz,1H),2.13(br.s,6H),2.10(br.s,3H),1.78(br.s,6H),1.28(d,J＝6.9Hz,6H)。¹³C NMR(CDCl₃,100MHz):δ159.33(d,J_C,F＝240Hz),150.47,145.50(d,J_C,F＝5.9Hz),137.28,136.00(d,J_C,F＝8.8Hz),131.87,130.86,125.47,123.65,115.67(d,J_C,F＝23.6Hz),113.95(d,J_C,F＝23.6Hz),98.98,57.03,41.03,37.57,36.85,33.66,29.03,23.84。

2- (3'- ((3r,5r,7r) -adamantan-1-yl) -5' -fluoro-4-isopropyl-2 '- (methoxymethyloxy) - [1,1' -biphenyl ] -2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane

To 4.70g (9.64mmol) of (3r,5r,7r) -1- (2' -bromo-5-fluoro-4 ' -isopropyl-2- (methoxymethoxy) - [1,1' -biphenyl at-80 deg.C](iii) -3-yl) adamantane to a solution in 100mL of anhydrous THF was added dropwise 3.86mL (9.64mmol) of 2.5Mn BuLi in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 2.33mL (12.5mmol) 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 and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 300mL) and the combined organic extracts were washed with Na ₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-ether ═ 10:1, volume). 5.10g (99%) of a colorless glassy solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.59(d,J＝1.9Hz),7.29(dd,J＝7.9,1.9Hz,1H),7.24(d,J＝7.9Hz),6.95(dd,J＝11.2,3.2Hz,1H),6.71(dd,J＝8.0,3.2Hz,1H),4.30–4.42(m,2H),3.20(s,3H),2.95(sept,J＝6.9Hz,1H),2.14(br.s,6H),2.08(br.s,6H),1.74-1.80(m,6H),1.28(d,J＝6.9Hz,6H),1.17(br.s,12H)。¹³C NMR(CDCl₃,100MHz):δ159.31(d,J_C,F＝240Hz),149.77(d,J_C,F＝2.4Hz),147.17,144.55(d,J_C,F＝6.6Hz),142.17,138.49(d,J_C,F＝8.1Hz),132.80,130.14,128.01,115.90(d,J_C,F＝22.5Hz),112.61(d,J_C,F23.6Hz),98.69,83.48,57.23,41.26,37.52,36.91,33.86,29.09,25.07 (wide), 24.26 (wide), 24.04.

2', 2' - (4-methoxypyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl ] -2-ol)

To a solution of 2.00g (3.74mmol) of 2- (3'- ((3r,5r,7r) -adamantan-1-yl) -5' -fluoro-4-isopropyl-2 '- (methoxymethoxy) - [1,1' -biphenyl]-2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 40mL of 1, 4-bis

To the solution in the alkane, 500mg (1.87mmol) of 2, 6-dibromo-4-methoxypyridine, 3.04g (9.35mmol) of cesium carbonate and 20mL of water were then added. The mixture obtained was purged with argonSwept for 10 min, then 216mg (0.187mmol) Pd (PPh) was added₃)₄. This mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3X 50mL) and the combined organic extracts were taken up in Na₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70mL) and the combined organic extracts were extracted with 5% NaHCO ₃Washing in Na₂SO₄Dried 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, vol). 1.31g (83%) of a mixture of the two isomers are obtained as a white foam.¹H NMR(CDCl₃400 MHz). delta.7.95 (s,1H),7.20-7.46(m,8H),6.73-6.84 and 6.06-6.09(2m,3H),6.59 and 6.51(2s,2H),3.63 and 3.46(2s,3H),2.95-3.10(2sept,2H),1.57-2.15(m,30H), 1.28-1.37 (m, 12H).¹³C NMR(CDCl₃,100MHz)δ166.41,166.10,159.62,159.46,157.73(d,J_C,F＝237Hz),157.62(d,J_C,F＝237Hz),148.99,148.74,148.66,148.29,139.95,139.89,139.39,138.30,133.96,131.90,131.14,129.34,128.13,128.03,127.84,127.59,127.03,114.54(d,J_C,F＝22.7Hz),114.19(d,J_C,F＝22.9Hz),113.01(d,J_C,F＝23.2Hz),112.70(d,J_C,F＝24.1Hz),108.57,108.45,55.25,54.97,40.16,39.96,37.00,36.93,36.89,36.83,36.68,33.83,33.65,28.99,28.90,23.99,23.93,23.76。

2- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol

To a solution of 8.40g (75.0mmol) of 4-fluorophenol and 13.5g (75.0mmol) of 3, 5-dimethyladamantan-1-ol in 150mL of dichloromethane was added dropwise a solution of 4.90mL (75.0mmol) of methanesulfonic acid and 5mL of acetic acid in 100mL of dichloromethane at room temperature for 1 hour. Mixing the obtained mixture inStirred at room temperature for 48 hours, then poured carefully into 300mL 5% NaHCO₃In (1). The crude product was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified using a Kugelrohr apparatus (1 mbar, 70 ℃) to give 14.2g (68%) of the title product as a pale yellow oil.¹H NMR(CDCl₃,400MHz):δ6.93(dd,J＝3.1,11.2Hz,1H),6.73(ddd,J＝3.1,7.4,8.6Hz,1H),6.55(dd,J＝4.9,8.6Hz),4.62(s,1H),2.16(dt,J＝3.1,6.3Hz,1H),1.91(m,2H),1.64-1.74(m,4H),1.35-1.45(m,4H),1.20(br.s,2H),0.87(s,6H)。¹³C NMR(CDCl₃,100MHz):δ158.49(J_F＝236Hz),150.19(J_F＝2.0Hz),137.69(J_F＝5.9Hz),117.12(J_F＝8.1Hz),114.13(J_F＝24.0Hz),112.57(J_F＝22.9Hz),50.92,46.44,43.05,38.70,38.48,31.38,30.84,29.90。

2-bromo-6- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol

To a solution of 14.2g (51.7mmol) of 2- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol in 200mL of dichloromethane was added dropwise a solution of 2.67mL (51.7mmol) of bromine in 100mL of dichloromethane at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours, then poured carefully into 200mL of 5% NaHCO ₃In (1). The crude product was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. 17.5g (96%) of a pale yellow solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.06(dd,J＝3.0,7.0Hz,1H),6.93(dd,J＝2.9,10.8Hz,1H),5.59(s,1H),2.16(m,1H),1.89(br.s,2H),1.63-1.73(m,4H),1.34-1.44(m,4H),1.19(br.s,2H),0.86(s,6H)。¹³C NMR(CDCl₃,100MHz):δ157.21(J_F＝241Hz),146.61(J_F＝2.8Hz),137.97(J_F＝6.1Hz),115.34(J_F＝25.8Hz),113.64(J_F＝23.6Hz),110.83(J_F＝10.9Hz),54.77,50.48,45.71,42.61,38.96,38.03,31.02,30.42,29.49。

1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3, 5-dimethyladamantane

2- (3- ((1R,3R,5S,7R) -3, 5-dimethyladamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane

To a solution of 14.0g (35.3mmol) of 1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3, 5-dimethyladamantane in 250mL of anhydrous THF at-80 deg.C was added 16.9mL (42.3mmol) of 2.5M nBuLi in hexane dropwise over 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 11.0mL (52.9mmol) of 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-bis Oxaborolidines. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 100mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was recrystallized from isopropanol. 9.65g (62%) of a white solid were produced.¹H NMR(CDCl₃,400MHz):δ7.19(dd,J＝7.7,3.3Hz,1H),7.08(dd,J＝11.0,3.3Hz,1H),5.11(s,2H),3.57(s,3H),2.13-2.16(m,1H),1.92(br.s,2H),1.66-1.77(m,4H),1.34(s,12H),1.33-1.44(m,4H),1.18(br.s,2H),0.85(s,6H)。¹³C NMR(CDCl₃,100MHz):δ159.41(d,J_C,F＝240Hz),157.64,143.65(d,J_C,F＝5.5Hz),119.53(d,J_C,F＝21.0Hz),117.42(d,J_C,F＝24.0Hz),101.19,84.00,57.86,50.91,47.15,43.03,39.51,39.03,31.48,30.90,30.00,24.78。

(1R,3R,5S,7R) -1- (2' -bromo-5-fluoro-4 ' -isopropyl-2- (methoxymethyloxy) - [1,1' -biphenyl ] -3-yl) -3, 5-dimethyladamantane

To a solution of 4.02g (9.09mmol) of 2- ((3r,5r,7r) -3-adamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan in 20mL of 1, 4-dioxaborolan

To the solution in alkane was then added 3.55g (10.9mmol) of 2-bromo-4-isopropyliodobenzene, 7.40g (22.7mmol) of cesium carbonate and 10mL of water. The resulting mixture was purged with argon for 10 minutes, and then 525mg (0.48mmol) of Pd (PPh) was added₃)₄. This mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-dichloromethane ═ 10:1 by volume). Yield 4.00g (86% ) A white solid.¹H NMR(CDCl₃,400MHz):δ7.52(d,J＝1.5Hz,1H),7.26(d,J＝7.7Hz,1H),7.20(dd,J＝7.8,1.6Hz,1H),7.03(dd,J＝11.1,3.2Hz,1H),6.78(dd,J＝7.9,3.2Hz,1H),4.47(m,1H),4.36(m,1H),3.18(s,3H),2.92(sept,J＝6.9Hz,1H),2.15-2.20(m,1H),1.92-1.99(m,2H),1.77-1.83(m,2H),1.65-1.71(m,2H),1.34-1.47(m,4H),1.27(d,J＝6.9Hz,6H),1.20(br.s,2H),0.88(s,6H)。¹³C NMR(CDCl₃,100MHz):δ159.24(d,J_C,F＝240Hz),150.45,150.18(d,J_C,F＝2.6Hz),144.82(d,J_C,F＝6.5Hz),137.25,135.86(d,J_C,F＝8.7Hz),131.90,130.88,125.50,123.59,115.76(d,J_C,F＝22.9Hz),113.96(d,J_C,F＝23.8Hz),99.13,57.10,50.89,47.25,47.20,43.01,39.47,39.28,33.65,31.50,30.95,30.02,23.86,23.84。

2- (3'- ((1R,3R,5S,7R) -3, 5-dimethyladamantan-1-yl) -5' -fluoro-4-isopropyl-2 '- (methoxymethoxy) - [1,1' -biphenyl ] -2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane

To a solution of 4.00g (7.76mmol) of (1R,3R,5S,7R) -1- (2' -bromo-5-fluoro-4 ' -isopropyl-2- (methoxymethoxy) - [1,1' -biphenyl at-80 deg.C]A solution of (E) -3-yl) -3, 5-dimethyladamantane in 50mL of anhydrous THF was added dropwise 3.17mL (7.91mmol) of 2.5M nBuLi in hexane for 20 min. The reaction mixture was stirred at this temperature for 1 hour, then 2.35mL (11.6mmol) 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 and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 100mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-ether ═ 10:1, volume). 3.97g (91%) of a colorless glassy solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.59(d,J＝1.8Hz,1H),7.29(dd,J＝7.9,1.9Hz,1H),7.24(d,J＝7.9Hz,1H),6.95(dd,J＝11.2,3.2Hz,1H),6.72(dd,J＝8.1,3.2Hz,1H),4.34(s,2H),3.22(s,3H),2.95(sept,J＝6.9Hz,1H),2.14-2.19(m,1H),1.72-1.98(m,6H),1.31-1.45(m,4H),1.28(d,J＝6.9Hz,6H),1.13-1.22(m,14H)。¹³C NMR(CDCl₃,100MHz):δ159.29(d,J_C,F＝240Hz),150.01(d,J_C,F＝2.6Hz),147.15,143.88(d,J_C,F＝6.5Hz),142.10(d,J_C,F＝1.7Hz),132.85,130.16,128.06,115.85(d,J_C,F＝22.7Hz),112.63(d,J_C,F23.6Hz),98.83,83.46,57.24,50.90,47.44 (wide), 43.04,39.69,39.20,33.85,31.52,30.94,30.08,25.20 (wide), 24.17 (wide), 24.04.

2', 2' - (pyridine-2, 6-diyl) bis (3- ((1R,3R,5S,7R) -3, 5-dimethyladamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl ] -2-ol)

To a solution of 3.97g (7.76mmol) of 2- (3'- ((1R,3R,5S,7R) -3, 5-dimethyladamantan-1-yl) -5' -fluoro-4-isopropyl-2 '- (methoxymethyloxy) - [1,1' -biphenyl ]]-2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 40mL of 1, 4-bis

To the solution in the alkane, 880mg (3.72mmol) of 2, 6-dibromopyridine, 6.40g (19.4mmol) of cesium carbonate and 20mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, and then 400mg (0.380mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3X 50mL) and the combined organic extracts were taken up in Na₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried and then evaporated to dryness. Will be provided withThe residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-ethyl acetate 10:1, vol). 2.11g (66%) of a mixture of the two isomers were obtained as a white foam. ¹H NMR(CDCl₃400MHz δ 7.87 and 7.04(2s,2H),7.63 and 7.42(2t,1H),7.21-7.38(m,7H),7.15 and 6.98(2d, J ═ 7.8Hz,2H),6.80(dd, J ═ 11.0,3.0Hz,1H),6.74(dd, J ═ 8.0,3.0Hz,1H),6.69(dd, J ═ 11.1,3.0Hz,1H),6.11(dd, J ═ 8.1,3.1Hz,1H),2.94-3.06(2sept,2H),1.41-1.85(m,12H),0.96-1.35(m,24H),0.78(s,3H),0.77(s,3H),0.72(s,3H), 3.72 (s, 3H).¹³C NMR(CDCl₃,100MHz)δ157.65(d,J_C,F＝238Hz),149.11,148.67,148.01,140.28,139.20,138.29,137.09,134.11,133.64,132.05,131.61,128.58,127.93,122.28,114.60(d,J_C,F＝22.3Hz),114.13(d,J_C,F＝23.0Hz),113.22(d,J_C,F＝23.4Hz),51.07,50.72,47.18,46.97,46.09,46.03,43.18,42.89,42.68,42.63,38.59,38.47,37.89,33.85,33.73,31.45,31.27,31.20,31.09,31.01,30.89,30.82,30.70,30.01,29.96。

4-fluoro-2- ((3r,5r,7r) -3, 5, 7-trimethyladamantan-1-yl) phenol

To a solution of 2.80g (25.0mmol) of 4-fluorophenol and 4.40g (22.7mmol) of 3, 5, 7-trimethyladamantan-1-ol in 30mL of dichloromethane was added dropwise a solution of 1.60mL (25.0mmol) of methanesulfonic acid and 2mL of acetic acid in 30mL of dichloromethane at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours, then poured carefully into 300mL of 5% NaHCO₃In (1). The crude product was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified using a Kugelrohr apparatus (1 mbar, 80 ℃) to give 3.9g (60%) of the title product as a pale yellow oil.¹H NMR(CDCl₃,400MHz):δ6.93(dd,J＝11.3,3.1Hz,1H),6.70-6.74(m,1H),6.55(dd,J＝8.6,5.0Hz,1H),4.87(br.s,1H),1.62(br.s,6H),1.00-1.18(m,6H),0.87(s,9H)。¹³C NMR(CDCl₃,100MHz):δ158.44(d,J_C,F＝237Hz),150.28(d,J_C,F＝2.0Hz),137.44(d,J_C,F＝5.9Hz),117.10(d,J_C,F＝8.3Hz),114.13(d,J_C,F＝24.0Hz),112.56(d,J_C,F＝23.0Hz),50.28,45.77,39.34,32.12,30.46。

2-bromo-4-fluoro-6- ((3r,5r,7r) -3, 5, 7-trimethyladamantan-1-yl) phenol

To a solution of 3.60g (12.5mmol) 4-fluoro-2- ((3r,5r,7r) -3, 5, 7-trimethyladamantan-1-yl) phenol in 20mL DMF at room temperature was added 2.22g (12.5mmol) NBS in one portion. The resulting mixture was stirred at room temperature for 48 hours, then poured carefully into 200mL of 5% NaHCO ₃In (1). The crude product was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-dichloromethane ═ 10:1 by volume). 3.00g (65%) of a white solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.06(dd,J＝6.9,3.0Hz,1H),6.94(dd,J＝10.8,3.0Hz,1H),5.60(s,1H),1.61(br.s,6H),1.06-1.18(m,6H),0.87(s,9H)。¹³C NMR(CDCl₃,100MHz):δ157.20(d,J_C,F＝241Hz),146.99(d,J_C,F＝3.0Hz),138.10(d,J_C,F＝6.0Hz),115.76(d,J_C,F＝26.0Hz),114.06(d,J_C,F＝23.6Hz),111.22(d,J_C,F＝10.9Hz),50.20,45.45,40.19,32.14,30.42。

(3r,5r,7r) -1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3, 5, 7-trimethyladamantane

To a solution of 2.20g (6.00mmol) 2-bromo-4-fluoro-6- ((3r,5r,7r) -3, 5, 7-trimethyladamantan-1-yl) phenol in 20mL anhydrous THF at room temperature was added 270mg (6.60mmol, 60% wt in mineralIn oil) sodium hydride. Thereafter, 630. mu.L (7.80mmol) of MOMCl were added in one portion. The reaction mixture was heated at 60 ℃ for 24 hours and then poured into 30mL of cold water. The crude product was extracted with 3X 20mL of dichloromethane. The combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. 2.50g (97%) of a white solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.14(dd,J＝6.9,3.1Hz,1H),6.99(dd,J＝10.9,3.1Hz,1H),5.19(s,2H),3.67(s,3H),1.62(br.s,6H),1.06-1.17(m,6H),0.88(s,9H)。¹³C NMR(CDCl₃,100MHz):δ159.50(d,J_C,F＝245Hz),150.15,146.11(d,J_C,F＝6.4Hz),118.17(d,J_C,F＝25.4Hz),117.67(d,J_C,F＝10.5Hz),114.05(d,J_C,F＝23.6Hz),100.08,57.93,50.07,46.53,40.65,32.25,30.46。

2- (5-fluoro-2- (methoxymethyloxy) -3- ((3r,5r,7r) -3, 5, 7-trimethyladamantan-1-yl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane

To a solution of 2.50g (5.89mmol) (3r,5r,7r) -1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3, 5, 7-trimethyladamantane in 30mL anhydrous THF was added 2.68mL (6.70mmol) of 2.5M nBuLi in hexane dropwise at-80 deg.C for 20 min. The reaction mixture was stirred at this temperature for 1 hour, then 1.84mL (7.12mmol) 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 and then poured into 30mL of water. The crude product was extracted with dichloromethane (3X 40mL) and the combined organic extracts were washed with Na ₂SO₄Dried and then evaporated to dryness. 2.70g (96%) of a white solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.20(dd,J＝7.6,3.2Hz,1H),7.08(dd,J＝10.9,3.3Hz,1H),5.11(s,2H),3.57(s,3H),1.65(br.s,6H),1.34(s,12H),1.06-1.17(m,6H),0.86(s,9H)。¹³C NMR(CDCl₃,100MHz):δ159.39(d,J_C,F＝240Hz),157.71(d,J_C,F＝2.0Hz),143.38(d,J_C,F＝5.7Hz),119.59(d,J_C,F＝21.0Hz),117.46(d,J_C,F＝24.0Hz),101.29,84.01,57.92,50.24,46.51,39.88,32.20,30.52,24.77。

(3r,5r,7r) -1- (2 '-bromo-5-fluoro-2- (methoxymethyloxy) - [1,1' -biphenyl ] -3-yl) -3, 5, 7-trimethyladamantane

To a solution of 2.70g (5.89mmol)2- (5-fluoro-2- (methoxymethyloxy) -3- ((3r,5r,7r) -3, 5, 7-trimethyladamantan-1-yl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan in 20mL 1, 4-bis

To the solution in alkane, 2.24g (7.90mmol) of 2-bromoiodobenzene, 5.00g (15.2mmol) of cesium carbonate and 10mL of water were then added. The resulting mixture was purged with argon for 10 minutes, and then 350mg (0.30mmol) of Pd (PPh) was added₃)₄. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-dichloromethane ═ 10:1 by volume). 2.50g (85%) of a white solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.73(d,J＝7.9Hz,1H),7.40-7.42(m,2H),7.26-7.30(m,1H),7.10(dd,J＝11.1,3.2Hz,1H),6.83(dd,J＝7.8,3.2Hz,1H),4.53(m,1H),4.42(m,1H),3.27(s,3H),1.73(s,6H),1.14–1.25(m,6H),0.95(s,9H)。¹³C NMR(CDCl₃,100MHz):δ159.22(d,J_C,F＝241Hz),150.23(d,J_C,F＝2.7Hz),140.01(d,J_C,F＝1.84Hz),135.75(d,J_C,F＝8.5Hz),133.03,132.12,129.11,127.24,123.75,115.69(d,J_C,F＝23.2Hz),114.14(d,J_C,F＝23.8Hz),99.24,57.16,50.21,46.52,40.13,32.21,30.55。

2- (5 '-fluoro-2' - (methoxymethyloxy) -3'- ((3r,5r,7r) -3, 5, 7-trimethyladamantan-1-yl) - [1,1' -biphenyl ] -2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan

To a solution of 2.34g (4.80mmol) of (3r,5r,7r) -1- (2 '-bromo-5-fluoro-2- (methoxymethoxy) - [1,1' -biphenyl at-80 deg.C]A solution of (E) -3-yl) -3, 5, 7-trimethyladamantane in 20mL of anhydrous THF was added dropwise with 2.00mL (5.04mmol) of a 2.5M solution of nBuLi in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 1.34mL (7.21mmol) 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 and then poured into 100mL of water. The crude product was extracted with dichloromethane (3X 100mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63 μm, eluent: hexane-ether ═ 10:1, volume). 2.50g (97%) of a colorless glassy solid are obtained.¹H NMR(CDCl₃,400MHz):δ7.76(d,J＝7.6Hz,1H),7.43(td,J＝7.5,1.5Hz,1H),7.31-7.35(m,2H),6.98(dd,J＝11.2,3.2Hz,1H),6.73(dd,J＝8.0,3.2Hz,1H),4.33(s,2H),3.25(s,3H),1.70(br.s,6H),1.08-1.21(m,18H),0.88(s,9H)。¹³C NMR(CDCl₃,100MHz):δ159.30(d,J_C,F＝240Hz),150.06(d,J_C,F＝2.4Hz),144.58,143.70(d,J_C,F＝6.6Hz),138.28(d,J_C,F＝8.3Hz),134.75,130.20,130.11,126.61,115.78(d,J_C,F＝22.7Hz),112.86(d,J_C,F23.6Hz),98.97,83.53,57.26,50.22,46.71,40.02,32.24,30.55,25.20 (wide), 24.12 (wide).

2', 2' - (pyridine-2, 6-diyl) bis (5-fluoro-3- ((3r,5r,7r) -3, 5, 7-trimethyladamantan-1-yl) - [1,1' -biphenyl ] -2-ol)

To a solution of 2.50g (4.80mmol) of 2- (5 '-fluoro-2' - (methyloxy) in waterMethoxymethoxy) -3'- ((3r,5r,7r) -3, 5, 7-trimethyladamantan-1-yl) - [1,1' -biphenyl]-2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane in 20mL of 1, 4-bis

To the solution in the alkane, 546mg (2.30mmol) of 2, 6-dibromopyridine, 4.02g (12.0mmol) of cesium carbonate and 10mL of water were then added. The resulting mixture was purged with argon for 10 minutes, then 304mg (0.240mmol) of Pd (PPh) was added₃)₄. This mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3X 50mL) and the combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70mL) and the combined organic extracts were extracted with 5% NaHCO₃Washing in Na₂SO₄Dried 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, vol). 690mg (37%) of a mixture of the two isomers were obtained as a white foam.¹H NMR(CDCl₃400 MHz). delta.7.37-7.54 (m,8H),6.65-7.04 and 6.29-6.32(m,9H),1.43(s,6H),1.22-1.40(m,6H),0.95-1.15(m,12H),0.78(s,9H),0.72(s, 9H).¹³C NMR(CDCl₃,100MHz)δ157.71(d,J_C,F＝240Hz),157.68(d,J_C,F＝240Hz),148.03,147.62(d,J_C,F＝2.0Hz),139.79,138.99,138.91,138.70,138.64,136.92,136.82,135.82,135.67,132.05,131.43,130.60,130.00,129.82,129.20,128.57,128.44,122.41,122.18,114.26(d,J_C,F＝22.7Hz),113.84(d,J_C,F＝23.0Hz),113.51(d,J_C,F＝23.4Hz),113.12(d,J_C,F＝23.7Hz),50.30,50.05,45.71,39.55,39.49,32.17,32.00,31.89,30.60,30.44。

Hafnium dimethyl [2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5-methyl- [1,1' -biphenyl ] -2-phenoxide) ] (Complex 1)

225mg (0.702mmol) of hafnium tetrachloride (0.702mmol) are introduced at 0 ℃ by syringe<0.5% Zr) to a suspension in 50mL of anhydrous toluene 1.10mL (3.16mmol) of 2.9M MeMgBr in ether were added in one portion. To the resulting suspension 500mg (0.702mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5-methyl- [1,1' -biphenyl were immediately added in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 473mg (73%) of a white-beige solid were produced. C₅₃H₅₇HfNO₂Analytical calculation of (a): c, 69.30; h, 6.26; n, 1.52. Measured value: c69.58; h, 6.39; and N is 1.40.¹H NMR(CDCl₃,400MHz):δ7.69(t,J＝7.8Hz,1H),7.54(td,J＝7.6,1.4Hz,2H),7.35(td,J＝7.5,1.3Hz,2H),7.30(dd,J＝7.8,1.2Hz,2H),7.10-7.14(m,4H),7.02(d,J＝2.3Hz,2H),6.69(dd,J＝2.3,0.6Hz,2H),2.23(s,6H),2.18-2.24(m,6H),2.04-2.14(m,12H),1.68-1.85(m,12H),-0.78(s,6H)。¹³C NMR(CDCl₃,100MHz)δ158.78,157.35,142.53,139.60,138.26,132.88,132.34,131.79,130.83,130.69,128.66,127.52,127.40,126.22,124.77,49.51,40.85,37.15,37.00,29.06,20.76。

Zirconium dimethyl [2', 2' - (pyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5-methyl- [1,1' -biphenyl ] -2-phenate) ] (Complex 3)

To a suspension of 131mg (0.562mmol) of zirconium tetrachloride in 50mL of anhydrous toluene at-30 ℃ by syringe was added 870uL (2.53mmol) of 2.9M in ether in one portion MeMgBr. To the resulting suspension was immediately added 400mg (0.562mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5-methyl- [1,1' -biphenyl in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 318mg (68%) of a beige solid are obtained. C₅₃H₅₇ZrNO₂Analytical calculation of (a): c, 76.58; h, 6.91; n, 1.69. Measured value: c76.89; h, 7.06; n1.52.¹H NMR(C₆D₆,400MHz):7.11-7.20(m,8H),7.02-7.04(m,2H),6.76(d,J＝2.2Hz,2H),6.39-6.50(m,3H),2.45-2.54(m,6H),2.32-2.37(m,6H),2.23(s,6H),2.17(br.s,6H),1.94-2.03(m,6H),1.80-1.89(m,6H),-0.10(s,6H)。¹³C NMR(CDCl₃,100MHz)δ159.31,158.31,143.44,139.58,138.60,133.65,133.59,133.18,131.42,131.13,129.36,128.54,128.06,127.20,124.43,42.89,41.95,38.18,37.85,30.01,21.41。

Hafnium dimethyl [2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 2)

To a solution of 118mg (0.369mmol) hafnium tetrachloride (0.369mmol) at 0 ℃ by syringe<0.5% Zr) in 50mL of dry toluene 570. mu.L (1.66mmol) of 2.9M MeMgBr in ether were added in one portion. To the resulting suspension 273mg (0.369mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl were immediately added in one portion ]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. Mixing the residueTrituration with 5mL of n-hexane afforded a precipitate which was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 240mg (69%) of a white-beige solid are obtained. C₅₅H₆₁HfNO₂Analytical calculation of (a): c, 69.79; h, 6.50; n, 1.48. Measured value: c70.08; h, 6.73; and (4) N1.35.¹H NMR(C₆D₆,400MHz):δ7.20(d,J＝2.4Hz,2H),7.12(d,J＝8.0Hz,2H),6.97(dd,J＝7.8,1.8Hz,2H),6.84(m,2H),6.74-6.76(m,2H),6.43-6.56(m,3H),2.45-2.53(m,6H),2.30-2.38(m,6H),2.23(s,6H),2.21(s,6H),2.15(br.s,6H),1.94-2.03(m,6H),1.76-1.84(m,6H),-0.03(s,6H)。¹³C NMR(C₆D₆,100MHz)δ159.99,158.16,140.99,139.42,139.03,137.75,133.71,133.23,133.14,132.44,131.03,129.60,128.29,126.99,125.20,51.24,41.67,38.04,37.81,30.04,21.41,21.39。

Zirconium dimethyl [2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl ] -2-phenolate) ] (complex 4)

To a suspension of 83mg (0.354mmol) zirconium tetrachloride in 30mL dry toluene at-30 deg.C was added 540. mu.L (1.59mmol) of 2.9M MeMgBr in ether in one portion via syringe. To the resulting suspension 262mg (0.354mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl were immediately added in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 193mg (63%) of a beige solid are produced. C ₅₅H₆₁ZrNO₂Analytical calculation of (a): c, 76.88; h, 7.16; n, 1.63. Measured value: c77.06; h, 7.43; n1.51.¹H NMR(C₆D₆,400MHz):δ7.19(d,J＝1.8Hz,2H),7.13(d,J＝7.8Hz,2H),6.96(ddd,J＝7.8,1.8,0.6Hz,2H),6.82(dd,J＝1.2,0.6Hz,2H),6.76(dd,J＝2.4,0.6Hz,2H),6.42-6.57(m,3H),2.48-2.55(m,6H),2.34-2.42(m,6H),2.22(s,6H),2.20(s,6H),2.15(br.s,6H),1.95-2.02(m,6H),1.77-1.84(m,6H),-0.20(s,6H)。¹³C NMR(C₆D₆,100MHz)δ159.46,158.49,140.84,139.40,138.49,137.69,133.62,133.59,133.51,132.31,130.93,129.66,128.89,128.22,127.09,126.03,124.74,42.91,41.72,38.14,37.80,30.04,21.42,21.38。

Hafnium dimethyl [2', 2' - (4-methoxypyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-phenoxide) ] (complex 7)

155mg (0.484mmol) of hafnium tetrachloride (0.484mmol) at 0 ℃ by means of a syringe<0.5% Zr) in 50mL of dry toluene 750. mu.L (2.18mmol) of 2.9M MeMgBr in ether were added in one portion. To the resulting suspension 400mg (0.484mmol) of 2', 2' - (4-methoxypyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl) were immediately added in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 338mg (68%) of a white-beige solid are obtained. C₆₀H₇₁HfNO₃Analytical calculation of (a): c, 69.78; h, 6.93; n,1.36. found: c70.04; h, 7.16; and N is 1.24. ¹H NMR(C₆D₆,400MHz):δ7.59(d,J＝2.6Hz,2H),7.19-7.21(m,2H),7.09-7.16(m,8H),6.08(s,2H),2.57-2.63(m,6H),2.55(s,3H),2.43-2.49(m,6H),2.21(br.s,6H),1.99-2.06(m,6H),1.83-1.90(m,6H),1.33(s,18H),-0.10(s,6H)。¹³C NMR(C₆D₆,100MHz)δ167.56,159.92,159.70,143.99,140.37,138.65,133.99,133.04,132.78,131.59,131.32,129.66,128.90,127.90,125.85,124.81,111.17,55.17,50.99,41.98,38.57,37.89,34.79,32.36,30.08。

Hafnium dimethyl [2', 2' - (4- (trifluoromethyl) pyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-phenoxide) ] (complex 8)

To 148mg (0.463mmol) of hafnium tetrachloride (0.463mmol) at 0 ℃ via syringe<0.5% Zr) in 50mL of dry toluene 720uL (2.10mmol) of 2.9M MeMgBr in ether was added in one portion. To the resulting suspension was immediately added 400mg (0.463mmol) of 2', 2' - (4- (trifluoromethyl) pyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 342mg (69%) of a yellow solid are produced. C₆₀H₆₈F₃HfNO₂Analytical calculation of (a): c, 67.31; h, 6.40; n,1.31. found: c67.65; h, 6.66; and (4) N1.20.¹H NMR(C₆D₆,400MHz):δ7.55(d,J＝2.6Hz,2H),7.07-7.18(m,4H),7.03(td,J＝7.4,1.6Hz,2H),6.99(d,J＝2.5Hz,2H),6.91(dd,J＝7.4,1.1Hz,2H),6.82(s,2H),2.47-2.53(m,6H),2.32-2.39(m,6H),2.17(br.s,6H),1.94-2.01(m,6H),1.80-1.89(m,6H),1.30(s,18H),-0.13(s,6H)。¹³C NMR(C₆D₆,100MHz)δ160.03,159.46,143.80,141.05,138.65,133.82,132.47,132.08,131.72,131.25,125.67,124.93,121.29(q,Jc,_F＝3.1Hz),51.49,41.94,38.49,37.79,34.78,32.23,29.98。

Hafnium dimethyl [2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 9)

155mg (0.485mmol) of hafnium tetrachloride (0.485mmol) at 0 ℃ via syringe<0.5% Zr) in 50mL of dry toluene 750. mu.L (2.20mmol) of 2.9M MeMgBr in ether were added in one portion. To the resulting suspension 400mg (0.485mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl were immediately added in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 287mg (57%) of a white-beige solid are obtained. C₆₁H₇₃HfNO₂Analytical calculation of (a): c, 71.08; h, 7.14; n, 1.36. Measured value: c71.31; h, 7.32; and N is 1.24.¹H NMR(C₆D₆,400MHz):δ7.58(d,J＝2.6Hz,2H),7.12(d,J＝7.8Hz,2H),7.03(d,J＝2.6Hz,2H),6.95(dd,J＝7.9,1.3Hz,2H),6.75(d,J＝0.7Hz,2H),6.39-6.52(m,3H),2.55-2.62(m,6H),2.40-2.48(m,6H),2.19(s,6H),2.19(br.s,6H),1.98-2.05(m,6H),1.78-1.86(m,6H),1.33(s,18H),-0.02(s,6H)。¹³C NMR(C₆D₆,100MHz)δ159.90,158.06,141.34,140.38,139.30,138.47,137.64,133.82,133.12,132.86,132.49,131.21,129.66,128.90,126.00,125.32,124.41,51.20,41.77,38.48,37.81,34.76,32.35,30.07,21.31。

Hafnium dimethyl [2', 2' - (4- (trifluoromethyl) pyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl ] -2-phenate) ] (complex 10)

135mg (0.421mmol) of hafnium tetrachloride (0.421mmol) at 0 ℃ via syringe <0.5% Zr) in 50mL of dry toluene 650. mu.L (1.89mmol) of 2.9M MeMgBr in ether were added in one portion. To the resulting suspension 400mg (0.421mmol) of 2', 2' - (4- (trifluoromethyl) pyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl) were immediately added in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 356mg (73%) of a yellow solid were produced. C₆₆H₈₀F₃HfNO₂Analytical calculation of (a): c, 68.64; h, 6.98; n, 1.21. Measured value: c68.88; h, 7.16; and (4) N1.13.¹H NMR(C₆D₆,400MHz):δ7.57(d,J＝2.6Hz,2H),7.19-7.22(m,4H),7.02(s,2H),6.98(d,J＝2.5Hz,2H),6.93(d,J＝1.7Hz,2H),2.91(sept,J＝6.9Hz,2H),2.53-2.60(m,6H),2.40-2.47(m,6H),2.15(br.s,6H),1.96-2.03(m,6H),1.77-1.85(m,6H),1.28(s,18H),1.23(d,J＝6.9Hz,6H),1.07(d,J＝6.9Hz,6H),0.00(s,6H)。¹³C NMR(C₆D₆,100MHz)δ160.39,159.75,149.13,141.82,140.98,138.51,134.19,132.28,129.29,125.96,124.61,121.84(q,Jc,_F＝3.0Hz),51.54,41.81,38.53,37.78,34.77,33.85,32.24,29.95,26.57,22.32。

Hafnium dimethyl [2', 2' - (4-methoxypyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 11)

140mg (0.440mmol) of hafnium tetrachloride (0.440mmol) at 0 ℃ by syringe<0.5% Zr) to a suspension in 50mL of anhydrous toluene 680. mu.L (1.98mmol) of a 2.9M solution of MeMgBr in ether were added in one portion. To the resulting suspension is neutralized Namely, 400mg (0.440mmol) of 2', 2' - (4-methoxypyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl was added in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 310mg (63%) of a white solid are obtained. C₆₆H₈₃HfNO₃Analytical calculation of (a): c, 70.98; h, 7.49; n,1.25. found: c71.24; h, 7.52; and N1.14.¹H NMR(C₆D₆,400MHz):δ7.60(d,J＝2.6Hz,2H),7.25(d,J＝8.1Hz,2H),7.18(m,2H),7.07(d,J＝2.5Hz,2H),7.02(d,J＝1.8Hz,2H),6.21(s,2H),2.98(sept,J＝6.8Hz,2H),2.60-2.67(m,6H),2.61(s,3H),2.48-2.56(m,6H),2.18(br.s,6H),2.01-2.08(m,6H),1.80-1.87(m,6H),1.31(s,18H),1.25(d,J＝6.8Hz,6H),1.12(d,J＝6.8Hz,6H),-0.02(s,6H)。¹³C NMR(C₆D₆,100MHz)δ167.36,160.15,160.03,148.56,141.83,140.28,138.50,134.24,133.36,132.93,129.58,128.24,126.19,124.50,111.80,55.16,51.06,41.85,38.60,37.87,34.79,33.77,32.38,30.03,26.54,22.31。

Hafnium dimethyl [2', 2' - (4- (trifluoromethyl) pyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-phenate) ] (complex 12)

144mg (0.448mmol) of hafnium tetrachloride (0.448mmol) are introduced via syringe at 0 DEG<0.5% Zr) in 50mL of anhydrous toluene 695. mu.L (2.02mmol) of 2.9M MeMgBr in ether are added in one portion. To the resulting suspension 400mg (0.448mmol) of 2', 2' - (4- (trifluoromethyl) pyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl were immediately added in one portion ]-2-phenol). The reaction mixture was stirred at room temperatureFor 4 hours, then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 398mg (81%) of a yellow solid are produced. C₆₂H₇₂F₃HfNO₂Analytical calculation of (a): c, 67.78; h, 6.61; n,1.27. found: c68.03; h, 6.74; and (4) N1.15.¹H NMR(C₆D₆,400MHz):δ7.55(d,J＝2.6Hz,2H),7.07(d,J＝7.9Hz,2H),6.95(d,J＝2.6Hz,2H),6.93(dd,J＝7.8,1.2Hz,2H),6.84(s,2H),6.69(d,J＝0.7Hz,2H),2.50-2.57(m,6H),2.37-2.45(m,6H),2.16(s,6H),2.15(br.s,6H),1.96-2.04(m,6H),1.78-1.86(m,6H),1.30(s,18H),-0.03(s,6H)。¹³C NMR(C₆D₆,100MHz)δ160.17,159.61,141.22,140.90,138.47,137.94,133.72,132.95,132.29,132.16,130.86,129.66,128.90,126.03,125.92,124.58,121.56(q,J^F＝3.5Hz),51.51,41.74,38.48,37.76,34.76,32.25,30.04,21.27。

Zirconium dimethyl [2', 2' - (4- (trifluoromethyl) pyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-phenate) ] (complex 13)

To a suspension of 105mg (0.448mmol) of zirconium tetrachloride in 50mL of anhydrous toluene at-30 ℃ was added 695. mu.L (2.02mmol) of 2.9M MeMgBr in ether in one portion via syringe. To the resulting suspension 400mg (0.448mmol) of 2', 2' - (4- (trifluoromethyl) pyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl were immediately added in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane The precipitate obtained is filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. Yielding 330mg (73%) of a yellow solid. C₆₂H₇₂F₃ZrNO₂Analytical calculation of (a): c, 73.62; h, 7.18; n, 1.38. Measured value: c73.90; h, 7.32; and N is 1.21.¹H NMR(C₆D₆,400MHz):δ7.54(d,J＝2.6Hz,2H),7.07(d,J＝7.8Hz,2H),6.95(d,J＝2.5Hz,2H),6.91(dd,J＝7.8,1.2Hz,2H),6.83(s,2H),6.67(m,2H),2.52-2.59(m,6H),2.39-2.47(m,6H),2.15(s,6H),2.15(br.s,6H),1.96-2.04(m,6H),1.79-1.86(m,6H),1.30(s,18H),-0.20(s,6H)。¹³C NMR(C₆D₆,100MHz)δ160.53,159.08,141.06,141.00,137.91,137.88,133.60,132.81,132.64,132.55,130.76,129.66,128.90,125.99,124.49,121.05(q,J^F＝3.0Hz),43.38,41.78,38.58,37.75,34.79,32.24,30.04,21.25。

Hafnium dimethyl [2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 14)

145mg (0.454mmol) of hafnium tetrachloride (0.454mmol) at 0 ℃ via syringe<0.5% Zr) in 50mL of dry toluene 704. mu.L (2.04mmol) of 2.9M MeMgBr in ether were added in one portion. To the resulting suspension was immediately added 400mg (0.454mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 333mg (67%) of a white solid were produced. C ₆₅H₈₁HfNO₂Analytical calculation of (a): c, 71.83; h, 7.51; n, 1.29. Measured value: c72.09; h, 7.67; and (4) N1.20.¹H NMR(C₆D₆,400MHz):δ7.58(d,J＝2.6Hz,2H),7.25(d,J＝8.1Hz,2H),7.17–7.19(m,2H),7.04(d,J＝2.6Hz,2H),6.92(d,J＝1.8Hz,2H),6.43-6.55(m,3H),2.95(sept,J＝6.9Hz,2H),2.56-2.63(m,6H),2.44-2.50(m,6H),2.17(br.s,6H),1.99-2.06(m,6H),1.78-1.86(m,6H),1.31(s,18H),1.25(d,J＝6.9Hz,6H),1.10(d,J＝6.9Hz,6H),0.00(s,6H)。¹³C NMR(C₆D₆,100MHz)δ158.67,157.62,147.92,140.68,139.28,138.93,137.17,133.04,132.32,131.59,128.97,127.37,125.20,125.15,123.24,49.62,40.65,37.42,37.04,34.15,33.03,31.72,29.08,26.02,21.86。

Hafnium dimethyl [2', 2' - (4-methoxypyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 15)

112mg (0.351mmol) of hafnium tetrachloride (0.351mmol) were injected via syringe at 0 deg.C<0.5% Zr) in 50mL of dry toluene 544. mu.L (1.56mmol) of 2.9M MeMgBr in ether were added in one portion. To the resulting suspension was immediately added 300mg (0.351mmol) of 2', 2' - (4-methoxypyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 284mg (76%) of a white solid are produced. C₆₂H₇₅HfNO₃Analytical calculation of (a): c, 70.20; h, 7.13; n, 1.32. Measured value: c70.45; h, 7.33; and N1.23. ¹H NMR(C₆D₆,400MHz):δ7.59(d,J＝2.6Hz,2H),7.12-7.14(m,2H),7.05(d,J＝2.6Hz,2H),6.95(dd,J＝7.9,1.2Hz,2H),6.85(m,2H),6.09(s,2H),2.63(s,3H),2.59-2.65(m,6H),2.44-2.53(m,6H),2.22(s,6H),2.19(br.s,6H),2.01-2.08(m,6H),1.80-1.87(m,6H),1.33(s,18H),0.00(s,6H)。¹³C NMR(C₆D₆,100MHz)δ166.82,159.09,158.73,140.36,139.21,137.23,137.08,132.94,132.42,131.61,131.51,130.47,123.29,110.90,55.69,49.23,40.68,37.47,37.02,34.15,31.72,29.16,21.01。

Hafnium dimethyl [2', 2' - (4-methoxypyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 16)

153mg (0.479mmol) of hafnium tetrachloride (0.479mmol) at 0 ℃ via syringe<0.05% Zr) in 50mL of anhydrous toluene 743. mu.L (2.16mmol) of 2.9M MeMgBr in ether was added in one portion. To the resulting suspension 400mg (0.479mmol) of 2', 2' - (4-methoxypyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl were immediately added in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 286mg (57%) of a white solid are produced. C₅₈H₆₅F₂HfNO₃Analytical calculation of (a): c, 66.94; h, 6.30; n,1.35. found: c67.23; h, 6.51; and (4) N1.25.¹H NMR(C₆D₆,400MHz):δ7.11-7.20(m,6H),7.02(m,2H),6.72(dd,J＝7.8,3.2Hz,2H),6.21(s,2H),2.94(sept,J＝6.8Hz,2H),2.52(s,3H),2.33-2.42(m,6H),2.20-2.30(m,6H),2.07(br.s,6H),1.87-1.95(m,6H),1.72-1.80(m,6H),1.24(d,J＝6.8Hz,6H),1.14(d,J＝6.8Hz,6H),-0.05(s,6H)。¹³C NMR(C₆D₆,100MHz)δ167.75,159.75,158.49,157.28(d,Jc,_F＝235Hz),149.31,141.11(d,Jc,_F＝5.7Hz),140.05(d,Jc,_F＝1.7Hz),133.81,133.47(d,Jc,_F＝7.7Hz),133.28,129.32,128.51,115.00(d,Jc,_F＝22.3Hz),114.58(d,Jc,_F＝23.0Hz),111.65,55.26,51.57,41.18,38.28,37.59,33.99,29.77,26.37,22.34。

Hafnium dimethyl [2', 2' - (4-methoxypyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -4'- (tert-butyl) -5-methyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 17)

165mg (0.515mmol) of hafnium tetrachloride (0.515mmol) are introduced at 0 ℃ via syringe<0.05% Zr) in 50mL of dry toluene 800. mu.L (2.32mmol) of 2.9M MeMgBr in ether were added in one portion. To the resulting suspension 440mg (0.515mmol) of 2', 2' - (4-methoxypyridin-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -4'- (tert-butyl) -5-methyl- [1,1' -biphenyl were immediately added in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 380mg (70%) of a white solid are obtained. C₆₂H₇₅HfNO₃Analytical calculation of (a): c, 70.20; h, 7.13; n, 1.32. Measured value: c70.46; h, 7.29; and (4) N1.25.¹H NMR(C₆D₆,400MHz):δ7.36(dd,J＝8.3,2.0Hz,2H),7.24(m,4H),7.20(d,J＝2.0Hz,2H),6.70(d,J＝2.0Hz,2H),6.26(s,2H),2.52-2.59(m,6H),2.47(s,3H),2.41-2.48(m,6H),2.19(s,6H),2.17(br.s,6H),1.98-2.06(m,6H),1.76-1.84(m,6H),1.34(s,18H),-0.06(s,6H)。¹³C NMR(C₆D₆,100MHz)δ167.46,160.77,160.29,151.37,141.42,139.12,134.02,133.98,133.05,129.71,129.56,126.86,125.47,112.05,55.00,51.36,41.67,38.26,37.81,35.15,31.74,29.98,21.34。

Hafnium dimethyl [2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -4'- (tert-butyl) -5-methyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 18)

124mg (0.388mmol) of hafnium tetrachloride (0.388mmol) were added via syringe at 0 ℃<0.05% Zr) in 50mL of dry toluene 600. mu.L (1.75mmol) of 2.9M MeMgBr in ether were added in one portion. To the resulting suspension was immediately added 320mg (0.388mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3- ((3r,5r,7r) -adamantan-1-yl) -4'- (tert-butyl) -5-methyl- [1,1' -biphenyl in one portion ]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. Yielding 301mg (75%) of a white solid. C₆₁H₇₃HfNO₂Analytical calculation of (a): c, 71.08; h, 7.14; n, 1.32. Measured value: c71.39; h, 7.27; n1.22.¹H NMR(C₆D₆,400MHz):δ7.35(dd,J＝8.3,2.0Hz,2H),7.22(d,J＝8.3Hz,2H),7.19(d,J＝2.0Hz,2H),7.14(d,J＝2.0Hz,2H),6.66(d,J＝1.7Hz,2H),6.45-6.53(m,3H),2.48-2.56(m,6H),2.37-2.45(m,6H),2.19(s,6H),2.16(br.s,6H),1.96-2.05(m,6H),1.75-1.84(m,6H),1.32(s,18H),0.07(s,6H)。¹³C NMR(C₆D₆,100MHz)δ160.12,158.83,151.36,141.36,139.48,139.01,133.84,132.99,129.65,129.57,126.93,125.76,125.54,51.54,41.59,38.17,37.75,35.12,31.69,29.92,21.33。

Hafnium dimethyl [2', 2' - (pyridine-2, 6-diyl) bis (3- ((1R,3R,5S,7R) -3, 5-dimethyladamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl ] -2-phenolate) ] (complex 19)

210mg (0.654mmol) of hafnium tetrachloride (0.654mmol) are introduced at 0 ℃ via syringe<0.05% Zr) in 50mL of dry toluene 900. mu.L (2.61mmol) of 2.9M MeMgBr in ether were added in one portion. To the resulting suspension was immediately added 562mg (0.654mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3- ((1R,3R,5S,7R) -3, 5-dimethyladamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 530mg (76%) of a white solid were produced. C ₆₁H₇₁F₂HfNO₂Analytical calculation of (a): c, 68.68; h, 6.71; n,1.31. found: c68.81; h, 6.99; and N1.23.¹H NMR(CD₂Cl₂,400MHz):δ7.77(t,J＝7.7Hz,1H),7.47(dd,J＝8.1,1.8Hz,2H),7.18(d,J＝8.1Hz,2H),7.16(d,J＝7.7Hz,2H),6.90-6.94(m,4H),6.49(dd,J＝7.9,3.2Hz,2H),2.97(sept,J＝6.9Hz,2H),2.60-2.67(m,2H),2.45-2.52(m,2H),2.00-2.05(m,2H),1.52-1.63(m,6H),1.33-1.42(m,4H),1.33(d,J＝6.9Hz,6H),1.30-1.34(m,2H),1.22(d,J＝6.9Hz,6H),1.11-1.24(m,6H),1.02-1.09(m,2H),0.91(s,6H),0.77(s,6H),-0.68(s,6H)。¹³C NMR(CD₂Cl₂,100MHz)δ157.97,157.89,156.47(d,Jc,_F＝234Hz),149.58,140.27,140.15(d,Jc,_F＝6.1Hz),139.42(d d,Jc,_F＝1.7Hz),133.12,133.03(d,Jc,_F＝7.9Hz),132.88,129.52,129.43,128.70,128.49,125.85,125.78,114.45(d,Jc,_F＝22.3Hz),113.65(d,Jc,_F＝23.2Hz),51.75,50.95,49.61,45.53,43.87,42.50,39.57,38.24,33.76,32.22,31.58,31.56,30.92,30.37,25.85,22.39。

Dimethylzirconium [2', 2' - (pyridine-2, 6-diyl) bis (3- ((1R,3R,5S,7R) -3, 5-dimethyladamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl ] -2-phenolate) ] (complex 20)

To a suspension of 135mg (0.581mmol) of zirconium tetrachloride in 50mL of anhydrous toluene at-30 deg.C was added by syringe 800. mu.L (2.32mmol) of 2.9M MeMgBr in ether in one portion. To the resulting suspension was added 500mg (0.581mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3- ((1R,3R,5S,7R) -3, 5-dimethyladamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl in one portion immediately]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. Yield 390mg (68%) of a white-beige solid. C₆₁H₇₁F₂ZrNO₂Analytical calculation of (a): c, 74.80; h, 7.31; n,1.43. found: c75.06; h, 7.64; and (3) N1.19. ¹H NMR(CD₂Cl₂,400MHz):δ7.76(t,J＝7.8Hz,1H),7.46(dd,J＝8.1,1.8Hz,2H),7.19(d,J＝8.0Hz,2H),7.15(d,J＝7.8Hz,2H),6.92(dd,J＝11.7,3.3Hz,2H),6.89(d,J＝1.8Hz,2H),6.51(dd,J＝8.0,3.3Hz,2H),2.97(sept,J＝6.9Hz,2H),2.65-2.73(m,2H),2.48-2.56(m,2H),2.00-2.06(m,2H),1.52-1.65(m,6H),1.33-1.43(m,6H),1.33(d,J＝6.9Hz,6H),1.22(d,J＝6.9Hz,6H),1.15-1.23(m,6H),1.06-1.14(m,2H),0.92(s,6H),0.79(s,6H),-0.42(s,6H)。¹³C NMR(CD₂Cl₂,100MHz)δ158.29,157.34,156.51(d,Jc,_F＝235Hz),149.53,140.25,139.61(d,Jc,_F＝6.1Hz),139.29(d,Jc,_F＝1.7Hz),133.42(d,Jc,_F＝7.9Hz),133.26,133.03,129.53,129.35,128.72,128.37,125.79,125.39,114.57(d,Jc,_F＝22.3Hz),113.61(d,Jc,_F＝23.2Hz),51.76,49.61,45.66,43.88,42.81,42.52,39.67,38.30,33.77,32.23,31.59,31.56,30.94,30.39。

Hafnium dimethyl [2', 2' - (pyridine-2, 6-diyl) bis (5-fluoro-3- ((3r,5r,7r) -3, 5, 7-trimethyladamantan-1-yl) - [1,1' -biphenyl ] -2-phenolate) ] (complex 21)

119mg (0.373mmol) of hafnium tetrachloride (0.373mmol) were added via syringe at 0 deg.C<0.05% Zr) in 50mL of dry toluene 510. mu.L (1.49mmol) of 2.9M MeMgBr in ether were added in one portion. To the resulting suspension was added immediately 300mg (0.373mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (5-fluoro-3- ((3r,5r,7r) -3, 5, 7-trimethyladamantan-1-yl) - [1,1' -biphenyl in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 × 20mL of hot toluene and the combined organic extracts were filtered through a pad of celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane and then dried in vacuo. 271mg (72%) of a white solid were produced. C₅₇H₆₃F₂HfNO₂Analytical calculation of (a): c, 67.74; h, 6.28; n,1.39. found: c67.98; h, 6.42; n1.37.¹H NMR(CD₂Cl₂,400MHz):δ7.79(t,J＝7.7Hz,1H),7.55(td,J＝7.5,1.5Hz,2H),7.49(td,J＝7.4,1.3Hz,2H),7.22(dd,J＝7.4,0.9Hz,2H),7.18(d,J＝7.8Hz,2H),7.11(dd,J＝7.4,0.9Hz,2H),6.97(dd,J＝11.7,3.3Hz,2H),6.52(dd,J＝7.8,3.3Hz,2H),1.74-1.80(m,6H),1.58-1.64(m,6H),1.17-1.24(m,6H),1.00-1.07(m,6H),0.88(s,18H),-0.74(s,6H)。¹³C NMR(CD₂Cl₂,100MHz)δ158.06,158.04,157.51,156.37(d,Jc,_F＝234Hz),141.79(d,Jc,_F＝1.7Hz),140.46,140.05(d,Jc,_F＝5.9Hz),139.99,132.98,132.90,132.79(d,Jc,_F＝7.9Hz),131.28,130.17,130.08,129.52,128.71,125.79,125.52,114.23(d,Jc,_F＝23.2Hz),114.02(d,Jc,_F＝22.4Hz),50.73,46.62,40.75,32.64,31.09。

Polymerization examples

Solvent, polymerization grade toluene and/or isohexane were supplied by ExxonMobil Chemical Company and purified by passing through a series of columns: from Labclear (Oakland, California) a) Two of 500cm³OxyClear series column, then packed and dried

Two 500cm molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company)³Tandem column, and packed with dry

Two 500cm molecular sieves (8-12 mesh; Aldrich Chemical Company)³Columns are connected in series.

1-octene (98%) (Aldrich Chemical Company) was stirred overnight over Na-K alloy, dried, and then filtered through Basic alumina (Aldrich Chemical Company, Brockman Basic 1). Tri (n-octyl) aluminum (TNOA) was purchased from Aldrich Chemical Company or Akzo Nobel and used as received.

Polymer grade ethylene was further purified by passing it through a series of columns: 500cm from Labclear (Oakland, California)³Oxycolar cylinder, then filled with dry

500cm of molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company)³Column, and packed with dried

500cm of molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company)³And (3) a column.

Polymer grade propylene was further purified by passing it through a series of columns: 2,250cm from Labclear³Oxycolar cylinder, then filled with

2,250cm molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company)³Column, then packed with

Two 5 tandem molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company) 00cm³Column, 500cm filled with Selexsorb CD (BASF)³Column, 500cm final packed with Selexsorb COS (BASF)³And (3) a column.

Methylaluminoxane (MAO) was purchased from Albemarle Corporation as 10 wt% in toluene. N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was purchased from Albemarle Corporation. All the complex and activator were added to the reactor as a dilute solution in toluene. The concentration of the solution of activator, scavenger and complex added to the reactor is selected such that 40-200 microliters of the solution is added to the reactor to ensure accurate delivery.

Reactor description and preparation

In an inert atmosphere (N)₂) Polymerization was carried out in a drying oven using an autoclave equipped with an external heater for temperature control, glass insert (for C)₂And C₂/C₈The test was carried out with the internal volume of the reactor being 23.5 mL; for C₃Test, 22.5mL), septum inlet, regulated supply of nitrogen, ethylene and propylene, and equipped with a disposable polyetheretherketone mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110 ℃ or 115 ℃ for 5 hours, then at 25 ℃ for 5 hours.

Ethylene Polymerization (PE) or ethylene/1-octene copolymerization (EO)

The reactor was prepared as described above and then purged with ethylene. Toluene (solvent unless otherwise specified), optionally 1-octene (0.1 mL when used) and optionally MAO were added via syringe at room temperature and atmospheric pressure. The reactor is then brought to process temperature (typically 80 ℃) and ethylene is added to process pressure (typically 75psig 618.5kPa or 200psig 1480.3kPa) while stirring at 800 rpm. An optional scavenger solution (e.g., TNOA in isohexane) is then added to the reactor via syringe under process conditions. An optional non-coordinating activator, such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, in solution (in toluene) is added to the reactor via syringe under process conditions, and then a procatalyst (i.e., complex or catalyst) solution (in toluene) is added via syringe under process conditions Into the reactor. Ethylene was admitted (via use of a computer controlled solenoid valve) to the autoclave during polymerization to maintain reactor gauge pressure (+/-2 psi). The reactor temperature was monitored and typically maintained within +/-1 ℃. By adding about 50psiO to the autoclave₂/Ar(5mol％O₂) The gas mixture was stopped for about 30 seconds. The polymerization is quenched after a predetermined cumulative amount of ethylene has been added or for a polymerization time of up to 30 minutes. The reactor was cooled and vented. The polymer was isolated after removal of the solvent in vacuo. The reported yields include the total weight of polymer and residual catalyst. The catalyst activity is reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g/mmol/hr).

Polymerization of propylene

The reactor was prepared as described above, then heated to 40 ℃ and purged with propylene gas at atmospheric pressure. Toluene (solvent, unless otherwise specified), optional MAO and liquid propylene (1.0mL) were added via syringe. The reactor was then heated to the process temperature (70 ℃ or 100 ℃) while stirring at 800 rpm. An optional scavenger solution (e.g., TNOA in isohexane) is then added to the reactor via syringe under process conditions. An optional non-coordinating activator, such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, in solution (in toluene) is then added to the reactor under process conditions via syringe, and then a procatalyst (i.e., complex or catalyst) solution (in toluene) is added to the reactor under process conditions via syringe. The reactor temperature was monitored and typically maintained within +/-1 ℃. By adding about 50psiO to the autoclave ₂/Ar(5mol％O₂) The gas mixture was stopped for about 30 seconds. The polymerization is quenched based on a predetermined pressure loss of about 8psi or a polymerization time of up to 30 minutes. The reactor was cooled and vented. The polymer was isolated after removal of the solvent in vacuo. The reported yields include the total weight of polymer and residual catalyst. Catalyst activity is typically reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g/mmol/hr).

Polymer characterization

For analytical tests, polymer sample solutions were prepared by dissolving the polymer in 1,2, 4-trichlorobenzene (TCB, purity 99 +%, from Sigma-Aldrich) containing 2, 6-di-tert-butyl-4-methylphenol (BHT, 99%, from Aldrich) for about 3 hours at 165 ℃ in a shaking oven. Typical concentrations of polymer in solution are 0.1 to 0.9mg/mL, with a BHT concentration of 1.25mg BHT/mL TCB. The sample was cooled to 135 ℃ for testing.

Using a solvent such as described in U.S. Pat. Nos. 6,491,816; 6,491,823, respectively; 6,475,391, respectively; 6,461,515, respectively; 6,436,292, respectively; 6,406,632, respectively; 6,175,409, respectively; 6,454,947, respectively; 6,260,407 and 6,294,388 (each of which is incorporated herein by reference) to perform high temperature size exclusion chromatography. Molecular weight (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distribution (MWD ═ Mw/Mn), which is sometimes also referred to as Polydispersity (PDI) of the Polymer, were measured by gel permeation chromatography using Symyx Technology GPC equipped with an evaporative light scattering detector and calibrated using polystyrene standards (Polymer Laboratories: polystyrene calibration kit S-M-10: Mp (peak Mw) between 5,000 and 3,390,000). Three Polymer Laboratories in series were used: PLgel 10 μm Mixed-B300X 7.5mm column, sample tested at an eluent flow rate of 2.0 mL/min (135 ℃ sample temperature, 165 ℃ oven/column) (250 μ L of polymer in TCB solution was injected into the system). No pillar extension correction (sparse correction) correction is used. Using those available from Symyx Technologies

The software or the Automation Studio software available from Freeslate performs the numerical analysis. The molecular weights obtained are relative to linear polystyrene standards.

Differential Scanning Calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point of the polymer. The samples were pre-annealed at 220 ℃ for 15 minutes and then allowed to cool to room temperature overnight. The sample was then heated to 220 ℃ at a rate of 100 ℃/min and then cooled at a rate of 50 ℃/min. The melting point was collected during the heating phase.

Table 1 shows the results obtained using catalyst complexes 1 to 21 and 23 to 27The result of ethylene polymerization of (1). General conditions: catalyst complex 25nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator 1.1 eq, 75psig ethylene, Al (N-octyl)₃500nmol, 80 ℃ and 5mL total volume.

TABLE 1 ethylene polymerization

TABLE 1 (continuation)

Table 2 shows the ethylene-octene copolymerization results obtained using catalysts 1 to 21 and 23 to 27. General conditions: catalyst complex 25nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator 27.5nmol, 0.1mL octene, Al (N-octyl)₃500nmol, 80 ℃, total volume 5mL, and ethylene 75 psi.

TABLE 2 ethylene-octene copolymerization

Table 2 (continuation)

Table 3 shows the ethylene-octene copolymerization results obtained using catalysts 1 to 21 and 23 to 27. General conditions: catalyst complex 25nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator 27.5nmol, 0.1mL octene, Al (N-octyl)₃500nmol, 80 ℃, total volume 5mL, and ethylene 200 psi.

TABLE 3 ethylene-octene copolymerization

Table 3 (continuation)

Table 4 shows the propylene polymerization results obtained for catalysts 1 to 28. General conditions: catalyst complex 15nmol (except for 25nmol for catalyst 26, 20nmol for catalysts 22 and 28), N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator 1.1 molar equivalents relative to catalyst complex, propylene 1ml, Al (N-octyl)₃500nmol, total volume 5 ml.

TABLE 4 polymerization of propylene

Table 4 (continuation)

Table 5 shows the propylene polymerization results obtained for catalysts 1 to 28. General conditions: catalyst complex 15nmol (with the exception of catalyst 26 25 nmol; with the exception of catalysts 22 and 28 20nmol), N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator 1.1 molar equivalents relative to catalyst complex, propylene 1ml, Al (N-octyl)₃500nmol, total volume 5 ml.

TABLE 5 polymerization of propylene

TABLE 5 (continuation)

All documents described herein, including any priority documents and/or test procedures, are incorporated by reference in their entirety for all jurisdictions in which the present invention is not inconsistent with this disclosure. It will be apparent from the foregoing summary and the specific embodiments that, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited thereby. Likewise, the term "comprising" is considered synonymous with the term "including". Likewise, whenever a composition, element, or group of elements precedes the transitional term "comprising," it is understood that the transitional term "consisting essentially of," consisting of, "selected from" or "being" the same composition or group of elements precedes the recited composition, element, or elements, and vice versa, is also contemplated.

Claims

1. A catalyst compound represented by the following formula (I):

wherein:

m is a group 3, 4, 5 or 6 transition metal or a lanthanide;

q is a group 14, 15 or 16 atom that forms a coordinate bond with metal M;

A¹QA^1'Is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, which connects A via a 3-atom bridge²Is connected to A²', wherein Q is the central atom of the 3-atom bridge, A¹And A¹' independently is C, N or C (R)²²) Wherein R is²²Selected from hydrogen, C₁-C₂₀Hydrocarbyl radical, C₁-C₂₀A substituted hydrocarbyl group;

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 more than 4;

and R¹And R²、R²And R³、R³And R⁴、R¹' and R²'、R²' and R³'、R³' and R⁴One or more pairs of' may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic or unsubstituted heterocyclic rings, each having 5, 6, 7 or 8 ring atoms, and wherein substituents on the rings may join to form additional rings;

any two L groups may be joined together to form a bidentate lewis base;

the X group may be joined to the L group to form a monoanionic bidentate group;

Any two X groups may be joined together to form a dianionic ligand group.

wherein:

m is a group 3, 4, 5 or 6 transition metal or a lanthanide;

each L is independently a lewis base;

each X is independently an anionic ligand;

n is 1, 2 or 3;

m is 0, 1 or 2;

n + m is not more than 4;

R¹、R²、R³、R⁴、R¹'、R²'、R³' and R⁴Each of' is independently hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R¹And R²、R²And R³、R³And R⁴、R¹' and R²'、R²' and R³'、R³' and R⁴One or more pairs of' may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic or unsubstituted heterocyclic rings, each having 5, 6, 7 or 8 ring atoms, and substituents on the rings may be joined to form additional rings; any two L groups may be joined together to form a bidentate lewis base;

the X group may be joined to the L group to form a monoanionic bidentate group;

any two X groups may be joined together to form a dianionic ligand group;

R⁵、R⁶、R⁷、R⁸、R⁵'、R⁶'、R⁷'、R⁸'、R¹⁰、R¹¹And R¹²Each of which is independently hydrogen, C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R⁵And R⁶、R⁶And R⁷、R⁷And R⁸、R⁵' and R⁶'、R⁶' and R⁷'、R⁷' and R⁸'、R¹⁰And R¹¹Or R¹¹And R¹²One or more pairs of (a) 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, and wherein substituents on the rings may join to form additional rings.

3. The catalyst compound of claim 1 or 2, wherein M is Hf, Zr or Ti.

4. The catalyst compound of claim 1, 2 or 3, wherein E and E' are each O.

5. The catalyst compound of claim 1, 2, 3 or 4 wherein R¹And R¹' independently is C₄-C₄₀A tertiary hydrocarbon group.

6. The catalyst compound of claim 1, 2, 3 or 4 wherein R¹And R¹' independently is C₄-C₄₀A cyclic tertiary hydrocarbon group.

7. The catalyst compound of claim 1, 2, 3 or 4 wherein R¹And R¹' independently is C₄-C₄₀Polycyclic tertiary hydrocarbon groups.

8. The catalyst compound of any one of claims 1 to 7, wherein each X is independently selected from: substituted or unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, hydride groups, amino groups, alkoxy groups, thio groups, phosphorus groups, halide groups, and combinations thereof (two X's may form part of a fused ring or ring system).

9. The catalyst compound of any one of claims 1 to 8, wherein each L is independently selected from: ethers, thioethers, amines, phosphines, diethyl ether, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, alkenes, alkynes, allenes, and carbenes, and combinations thereof, optionally two or more L may form part of a fused ring or ring system.

10. The catalyst compound of claim 1 wherein M is Zr or Hf, Q is nitrogen, A¹And A¹'are both carbon, E and E' are both oxygen, and R¹And R¹' all are C₄-C₂₀A cyclic tertiary alkyl group.

11. The catalyst compound of claim 1 wherein M is Zr or Hf, Q is nitrogen, A¹And A¹'are both carbon, E and E' are both oxygen, and R¹And R¹' are all adamantan-1-yl or substituted adamantan-1-yl.

12. The catalyst compound of claim 1 wherein M is Zr or Hf, Q is nitrogen, A¹And A¹'are both carbon, E and E' are both oxygen, and R¹And R¹' all are C₆-C₂₀And (4) an aryl group.

13. The catalyst compound of claim 1 wherein Q is nitrogen and A¹And A¹' are all carbon, R¹And R¹'both are hydrogen, E and E' are both NR⁹Wherein R is⁹Is selected from C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Substituted hydrocarbyl or heteroatom containing groups.

14. The catalyst compound of claim 1 wherein Q is carbon and A¹And A¹'both are nitrogen and E' are both oxygen.

15. The catalyst compound of claim 1 wherein Q is carbon and A¹Is nitrogen, A¹' is C (R)²²) E and E' are both oxygen, wherein R²²Selected from hydrogen, C₁-C₂₀Hydrocarbyl radical, C₁-C₂₀A substituted hydrocarbyl group.

16. The catalyst compound of claim 1 wherein the heterocyclic lewis base is selected from the group represented by the formula:

17. The catalyst compound of claim 2 wherein M is Zr or Hf, E and E' are both oxygen, R¹And R¹' all are C₄-C₂₀A cyclic tertiary alkyl group.

18. The catalyst compound of claim 2 wherein M is Zr or Hf, E and E' are both oxygen, R¹And R¹' are both adamantan-1-yl or substituted adamantan-1-yl.

19. The catalyst compound of claim 2 wherein M is Zr or Hf, E and E' are both oxygen, R¹、R¹'、R³And R³Each of' is an adamantan-1-yl or substituted adamantan-1-yl group.

20. The catalyst compound of claim 2 wherein M is Zr or Hf, E and E' are both oxygen, R¹And R¹' all are C₄-C₂₀Cyclic tertiary alkyl radical, R⁷And R⁷' all are C₁-C₂₀An alkyl group.

21. The catalyst compound of claim 2 wherein M is Zr or Hf, E and E' are both O, R¹And R¹' all are C₄-C₂₀Cyclic tertiary alkyl radical, R⁷And R⁷' all are C₁-C₂₀An alkyl group.

22. The catalyst compound of claim 2 wherein M is Zr or Hf, and E' are both Is O, R¹And R¹' all are C₄-C₂₀Cyclic tertiary alkyl radical, R⁷And R⁷' all are C₁-C₃An alkyl group.

23. The catalyst compound of claim 1, wherein the catalyst compound is represented by one or more of the following formulas:

24. a catalyst system comprising an activator and the catalyst compound of any one of claims 1-23.

25. The catalyst system of claim 24, wherein the activator comprises an alumoxane or a non-coordinating anion.

26. The catalyst system of claim 24, wherein the activator is soluble in a non-aromatic hydrocarbon solvent.

27. The catalyst system of claim 24, wherein the catalyst system is free of aromatic solvents.

28. The catalyst system of claim 24, wherein the activator is represented by the formula:

29. The catalyst system of claim 24, wherein the activator is represented by the formula:

wherein:

e is nitrogen or phosphorus;

d is 1, 2 or 3; k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6; n-k ═ d;

R^1′、R^2′and R^3′Independently C optionally substituted by one or more alkoxy, silyl, halogen atoms or halogen-containing groups ₁-C₅₀A hydrocarbon group,

mt is an element selected from group 13 of the periodic table; and

each Q is independently a hydrogen radical, a bridged or unbridged dialkylamido group, a halo group, an alkoxy group, an aryloxy group, a hydrocarbyl group, a substituted hydrocarbyl group, a halocarbyl group, a substituted halocarbyl group, or a halo-substituted hydrocarbyl group.

30. The catalyst system of claim 24, wherein the activator is represented by the formula:

wherein A is^d-Is a non-coordinating anion having a charge d-; d is an integer from 1 to 3, (Z)_d ⁺By one or more of the following formulaeRepresents:

31. the catalyst system of claim 24, wherein the activator is one or more of the following:

N-methyl-4-nonadecyl-N-octadecylanilinium tetrakis (pentafluorophenyl) borate,

N-methyl-4-nonadecyl-N-octadecylanilinium tetrakis (perfluoronaphthyl) borate,

dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate,

dioctadecyl methylammonium tetrakis (perfluoronaphthyl) borate,

n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

Triphenylcarbenium tetrakis (pentafluorophenyl) borate

Trimethyl ammonium tetrakis (perfluoronaphthyl) borate,

triethylammonium tetrakis (perfluoronaphthyl) borate,

tripropylammonium tetrakis (perfluoronaphthyl) borate,

Tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate,

tri (tert-butyl) ammonium tetrakis (perfluoronaphthyl) borate,

n, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate,

n, N-diethylanilinium tetrakis (perfluoronaphthyl) borate,

n, N-dimethyl- (2,4, 6-trimethylanilinium) tetrakis (perfluoronaphthyl) borate,

tetrakis (perfluoronaphthyl) boronic acid

Triphenylcarbon tetrakis (perfluoronaphthyl) borate

Tetrakis (perfluoronaphthyl) borate triphenylphosphine

Tetrakis (perfluoronaphthyl) borate triethylsilane

Tetrakis (perfluoronaphthyl) boratabenzene (diazo)

)，

Trimethyl ammonium tetrakis (perfluorobiphenyl) borate,

triethylammonium tetra (perfluorobiphenyl) borate,

tripropylammonium tetrakis (perfluorobiphenyl) borate,

tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate,

tri (tert-butyl) ammonium tetrakis (perfluorobiphenyl) borate,

n, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate,

n, N-diethylanilinium tetrakis (perfluorobiphenyl) borate,

n, N-dimethyl- (2,4, 6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate,

tetra (perfluorobiphenyl) boronic acid

Triphenylcarbon tetrakis (perfluorobiphenyl) borate

Tetrakis (perfluorobiphenyl) borate triphenylphosphine

Tetra (perfluorobiphenyl)Boric acid triethylsilane

Tetrakis (perfluorobiphenyl) borate benzene (diazonium)

)，

[ 4-tert-butyl-PhNMe 2H ] [ (C6F3(C6F5)2)4B ],

The reaction product of trimethyl ammonium tetraphenyl borate,

the triethyl ammonium tetraphenyl borate is a compound of the formula,

tri (n-butyl) ammonium tetraphenyl borate,

tri (tert-butyl) ammonium tetraphenylborate,

n, N-dimethylanilinium tetraphenylborate,

n, N-diethylanilinium tetraphenylborate,

n, N-dimethyl- (2,4, 6-trimethylanilinium) tetraphenylborate,

tetraphenylboronic acids

Triphenylcarbon tetraphenylborate

Tetraphenylboronic acid triphenylphosphine

Tetraphenylboronic acid triethylsilane

Tetraphenylboronic acid benzene (diazo)

)，

Trimethyl ammonium tetrakis (pentafluorophenyl) borate,

triethylammonium tetrakis (pentafluorophenyl) borate,

tripropylammonium tetrakis (pentafluorophenyl) borate,

tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate,

tris (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate,

n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

n, N-diethylanilinium tetrakis (pentafluorophenyl) borate,

n, N-dimethyl- (2,4, 6-trimethylanilinium) tetrakis (pentafluorophenyl) borate,

tetrakis (pentafluorophenyl) borate

Triphenylcarbenium tetrakis (pentafluorophenyl) borate

Triphenylphosphine tetrakis (pentafluorophenyl) borate

Triethylsilane tetrakis (pentafluorophenyl) borate

Tetrakis (pentafluorophenyl) borate benzene (diazo)

)，

Trimethylammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

triethylammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

Tripropylammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

tri (n-butyl) ammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

dimethyl (tert-butyl) ammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

n, N-dimethylanilinium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

n, N-diethylanilinium tetrakis (2,3,4, 6-tetrafluorophenyl) borate,

tetrakis (2,3,4, 6-tetrafluorophenyl) boronic acid

Triphenylcarbenium tetrakis (2,3,4, 6-tetrafluorophenyl) borate

Triphenylphosphine tetrakis (2,3,4, 6-tetrafluorophenyl) borate

Triethylsilane tetrakis (2,3,4, 6-tetrafluorophenyl) borate

Tetrakis (2,3,4, 6-tetrafluorophenyl) borate benzene (diazonium)

)，

Trimethylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

triethylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

tripropylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

tri (n-butyl) ammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

Tri (tert-butyl) ammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

n, N-dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

N, N-diethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

Triphenylcarbenium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

Tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate triphenylphosphine

Triethylsilane tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

Tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate benzene (diazonium)

)，

Di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate,

dicyclohexylammonium tetrakis (pentafluorophenyl) borate,

tris (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate

Tris (2, 6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate

Triphenylcarbenium tetrakis (perfluorophenyl) borate

A salt of tetrakis (pentafluorophenyl) borate, or a salt thereof,

4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluoropyridine, and

triphenylcarbenium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

32. A process for polymerizing olefins comprising contacting one or more olefins with the catalyst system of any of claims 23-31.

33. The process of claim 32, wherein the process is carried out at a temperature of from about 0 ℃ to about 300 ℃, at a pressure of from about 0.35MPa to about 10MPa, and for a time of up to 300 minutes.

34. The method of claim 32, further comprising obtaining a polymer.

35. The process of claim 32, wherein the olefin comprises one or more substituted or unsubstituted C ₂-C₄₀An alpha-olefin.