Metallocene catalyst compounds having ferrocenyl substituents

Abstract

In some embodiments, the catalyst compound is represented by formula (I): M is a Group 3-5 metal, a lanthanide metal atom, or an actinide metal atom. E is a substituted polycyclic arenyl ligand bonded to M, substituted with at least one ferrocenyl substituent bonded to the aromatic six-membered ring of the polycyclic arenyl ligand. A is a monoanionic ligand bonded to M. n is 0 or 1. T is bonded to A and E and is a bridging group containing a Group 13, 14, 15, or 16 element, and is present when n is 1 and absent when n is zero. Each occurrence of X is independently a monovalent anionic ligand, or two Xs are joined together and bonded to M to form a metallocycle ring, or two Xs are joined together to form a chelating ligand, a diene ligand, or an alkylidene ligand.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 484,899, filed February 14, 2023, the disclosure of which is incorporated herein by reference in its entirety. FIELD OF THE DISCLOSURE The present disclosure relates to metallocene catalyst compounds having ferrocenyl substituents, catalyst systems containing such compounds, and their uses. [Background technology]

[0002] Olefin polymerization catalysts are of great utility in industry, and polyolefins are widely used commercially due to their stable physical properties. Therefore, there is interest in finding new catalysts that will increase the commercial viability of catalysts and enable the production of polymers with improved properties. For example, various types of polyethylene, including high-density, low-density, and linear low-density polyethylene, are commercially useful. Polyolefins, including polyethylene or polypropylene, can be synthesized using transition metal catalyst compounds, which are typically activated with an activator containing an alumoxane or non-coordinating anion. The use of catalyst compounds in combination with activators creates catalyst systems that can offer the ability to tailor polyolefin properties, including polymer structure and composition, such as molecular weight, comonomer incorporation, melting temperature, and / or (in the case of polypropylene) stereoregularity. For example, isotacticity provides increased crystallinity in polypropylene polymer chains, which provides increased mechanical strength compared to atactic polypropylene equivalents. The ability to modify polyolefin properties is a long-sought goal in the field of polymer synthesis. Improved polymerization catalysts continue to be needed.

[0003] Improvements in polymerization catalysts can result from catalysts with high activity that can produce polyolefins with high molecular weight, controllable molecular weight, narrow polydispersity index, or high comonomer incorporation. Catalysts capable of one or more of the above improvements are beneficial, but it is even more beneficial when a catalyst combines several improvements over previous catalysts or catalyst systems into an overall benefit. For example, polyolefins with high molecular weights generally have more desirable mechanical properties than their lower molecular weight counterparts. However, high molecular weight polyolefins can be difficult to process and expensive to produce. Furthermore, polyolefins such as polyethylene can have comonomers such as octene incorporated into the polyethylene backbone, which can improve processability while maintaining most, if not all, of the mechanical property advantages offered by high molecular weight. The comonomer content of a polyolefin (e.g., the weight percent of comonomer incorporated into the polyolefin backbone) affects the properties of the polyolefin (and the composition of the copolymer) and is influenced by the polymerization catalyst. Furthermore, even if desired polymer properties can be obtained, conventional catalysts used in the formation of polyolefins often have low catalytic activity. There is a need for new and improved catalyst compounds and catalyst systems capable of forming polyolefins with high activity, producing polyolefins with properties such as controllable molecular weight, high melting point, high comonomer incorporation, narrow polydispersity index, and / or isotacticity.

[0004] References cited in the information disclosure statement (37 CFR 1.97(h)): CN107903346;KR2017087131;DE4417542;US5,521,265;EP673946;CN107814861;Y. Zhong, et al., Dalton Transactions, 346-354, 50(1), 2021;C. Elschenbroich, et al., Polyhedron, 300-305, 79, 2014;K. Unverhau, et al., Dalton Transactions, 3724-3736, 40(14), 2011;A. Jakob, et al., J. Org. Chem., 3542-3547, 694(22), 2009;P. Witte, et al., Organometallics, 4147-4155, 18(20), 1999;K. Kimura, et al., Chem. Lett., 571-572, (7), 1998;P. Scott, et al., Organometallics, 3094-3101, 12(8), 1993. Summary of the Invention

[0005] FIELD OF THE DISCLOSURE The present disclosure relates to metallocene catalyst compounds having ferrocenyl substituents, catalyst systems containing such compounds, and their uses. In some embodiments, the catalyst compound is represented by formula (I): [ka] M is a Group 3-5 metal, a lanthanide metal atom, or an actinide metal atom. E is a substituted polycyclic arene ligand bonded to M and is substituted with at least one ferrocenyl substituent bonded to the aromatic six-membered ring of the polycyclic arene ligand. A is a monoanionic ligand bonded to M. n is 0 or 1. T is bonded to A and E and is a bridging group containing a Group 13, 14, 15, or 16 element, and is present when n is 1 and absent when n is zero. Each occurrence of X is independently a monovalent anionic ligand, or two Xs are joined together and bonded to M to form a metallocycle ring, or two Xs are joined together to form a chelating ligand, a diene ligand, or an alkylidene ligand. Each occurrence of L is independently a Lewis base, or two Ls are joined together and bonded to M to form a bidentate Lewis base. X may be linked to L to form a monoanionic bidentate group. y is 1, 2, or 3. w is 0, 1, or 2. y+w is 4 or less. In yet another aspect, embodiments of the present disclosure provide a catalyst system comprising an activator and a catalyst compound of the present disclosure. In yet another aspect, embodiments of the present disclosure provide a polymerization method comprising the step of: a) contacting one or more olefin monomers with a catalyst system comprising: i) an activator; and ii) a catalyst compound of the present disclosure.

[0006] definition For purposes of this disclosure and the claims herein, the following definitions and conventions apply. For the purposes of this disclosure, the numbering scheme for the Periodic Table Groups will be used as set forth in Chemical and Engineering News, 63(5), pg. 27 (1985). The following abbreviations may be used herein: Fc is ferrocenyl, Me is methyl, Et is ethyl, Ph is phenyl, tBu is tertiary butyl, PDI is polydispersity index, MAO is methylalumoxane, SMAO is supported methylalumoxane, NMR is nuclear magnetic resonance, ppm is parts per million, THF is tetrahydrofuran, and RPM is revolutions per minute.

[0007] As used herein, an olefin polymerization catalyst refers to any catalyst, such as an organometallic complex or compound, capable of coordinate polymerization addition, in which successive monomers are added to a monomer chain at an organometallic active center.

[0008] The terms "substituent," "radical," "group," and "moiety" may be used interchangeably. An "olefin," alternatively referred to as an "alkene," is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification, 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 described as having an "ethylene" content of 35% to 55% by weight, it is understood that the mer units in the copolymer are derived from ethylene in a polymerization reaction, and that the derived units are present in an amount of 35% to 55% by weight based on the weight of the copolymer. A "polymer" has two or more mer units, which may be the same or different. A "homopolymer" is a polymer having the same mer units. A "copolymer" is a polymer having two or more mer units that are different from one another. A "terpolymer" is a polymer having three mer units that are different from one another. The term "different," when used to refer to mer units, indicates that the mer units differ from one another by at least one atom, or are isomerically different. Thus, as used herein, the definition of copolymer includes terpolymers. An "ethylene polymer" or "ethylene copolymer" (both of which are examples of "polyethylene") is a polymer or copolymer containing at least 50 mol % of ethylene-derived units. A "propylene polymer" or "propylene copolymer" (both of which are examples of "polypropylene") is a polymer or copolymer containing at least 50 mol % of propylene-derived units, etc. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mol % of ethylene-derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mol % of propylene-derived units, etc. As used herein, "polyethylene" may include "ethylene homopolymer," "ethylene copolymer," or a combination thereof. "Polypropylene" may include "propylene homopolymer," "propylene copolymer," or a combination thereof.

[0009] The term "alpha-olefin" refers to an olefin having a terminal carbon-carbon double bond in its structure ((R"R"')-C=CH2, where R" and R'" can independently be hydrogen or any hydrocarbyl group, e.g., R" is hydrogen and R"' is an alkyl group). A "linear alpha-olefin" is an alpha-olefin as defined in this paragraph where R" is hydrogen and R"' is hydrogen or a linear alkyl group. For the purposes of this disclosure, ethylene is considered an alpha-olefin.

[0010] As used herein, and unless otherwise specified, "C n " refers to a hydrocarbon having n carbon atoms per molecule, where n is a positive integer. The term "hydrocarbon" refers to a class of compounds containing hydrogen bonded to carbon and encompasses mixtures of hydrocarbon compounds (saturated and / or unsaturated), including (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds with different values ​​of n. Similarly, "C m -C y " group or compound refers to a group or compound containing a total of m to y carbon atoms. Thus, C1-C 50 Alkyl refers to alkyl groups containing a total of from about 1 to about 50 carbon atoms.

[0011] Unless otherwise specified (e.g., in the definitions of "substituted hydrocarbyl," "substituted aromatic," etc.), the term "substituted" means that at least one hydrogen atom has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, such as a halide (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 (in the formula, each R * are independently hydrocarbyl or halocarbyl radicals, 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 at least one heteroatom is inserted within the hydrocarbyl ring.

[0012] The term "substituted hydrocarbyl" refers to a group in which at least one hydrogen atom of a hydrocarbyl radical has been replaced with at least one heteroatom (e.g., a halide, 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 (in the formula, each R * are independently hydrocarbyl or halocarbyl radicals, 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 at least one heteroatom or heteroatom-containing group (e.g., a functional group, e.g., -NR * -, -O-, -Se-, -Te-, -PR * - , -AsR * - , -SbR * - , -S-, -BR * 2-, -SiR * 2-, -GeR * 2-, -SnR * 2-, -PbR *2-(wherein, each R * is as defined above)) is inserted within the hydrocarbyl chain or ring. Substitutions, unless specifically included, exclude ferrocenyl substituents. The term "substituted aromatic" means an aromatic group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. The term "substituted phenyl" means a phenyl group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0013] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" may be used interchangeably and are defined to mean a group containing only hydrogen and carbon atoms. For example, a hydrocarbyl may be a C-C alkyl group that may be linear, branched, or cyclic. 100 It may be a radical, and if cyclic, may be aromatic or non-aromatic. Examples of such radicals may include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and aryl groups such as phenyl, benzyl, naphthyl.

[0014] The terms "alkoxy" and "alkoxide" refer to an alkyl or aryl group attached to an oxygen atom, e.g., an alkyl ether or aryl ether group / radical attached to an oxygen atom, where the alkyl / aryl group is C1-C 10 The alkyl group may be linear, branched, or cyclic. The alkyl group may be saturated or unsaturated. Examples of suitable alkoxy radicals may include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, and phenoxy.

[0015] The term "alkenyl" refers to a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more double bonds. These alkenyl radicals may be substituted. Examples of suitable alkenyl radicals include ethenyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cyclooctenyl, including substituted analogs thereof.

[0016] The terms "alkyl radical," "alkyl group," and "alkyl" are used interchangeably throughout this disclosure. For purposes of this disclosure, an "alkyl radical" is a C-C alkyl group that may be linear, branched, or cyclic. 100

[0023] The term "alkyl" refers to a group selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like. Some examples of alkyl include 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-ethylbutyl, 1,3-dimethylbutyl, 1-methyl-1-ethylbutyl, 1,1-diethylbutyl, 1-propylpentyl, 1-phenylethyl, i-propyl, 2-butyl, sec-pentyl, sec-hexyl, and the like.

[0017] The term "aryl" or "aryl group" refers to aromatic rings and substituted variations thereof, such as phenyl, 2-methyl-phenyl, xylyl, and 4-bromo-xylyl. Similarly, "heteroaryl" refers to an aryl group in which one ring carbon atom (or two or three ring carbon atoms) is replaced with a heteroatom, such as N, O, or S. As used herein, the term "aromatic" also refers to pseudo-aromatic heterocycles, which are heterocyclic substituents with properties and structure (nearly planar) similar to aromatic heterocyclic ligands but which are not aromatic by definition; similarly, the term aromatic also refers to substituted aromatics.

[0018] For purposes of naming, the following numbering scheme is used for cyclopentadienyl, indenyl, fluorenyl, cyclopenta[b]naphthalenyl (also called benz[e]indenyl), cyclopenta[a]naphthalenyl (also called benz[f]indenyl), tetrahydro-s-indacenyl, and tetrahydro-as-indacenyl. The numbering scheme indicates the position along the ring to which a moiety may be attached. For example, a moiety such as a phenanthridinyl moiety may be attached to the 4-position of a cyclopentadienyl. Indenyl can be considered a cyclopentadienyl with a fused benzene ring. Similarly, fluorenyl can be considered a cyclopentadienyl with two fused benzene rings fused to the cyclopentadienyl ring. Each of the following structures is depicted and named as an anion: [ka]

[0019] The partially hydrogenated polycyclic arenyl ligands retain the numbering scheme of the parent polycyclic arenyl ligand, i.e., the numbering scheme defined for the indenyl, fluorenyl, cyclopenta[b]naphthalenyl, cyclopenta[a]naphthalenyltetrahydro-s-indenyl, and tetrahydro-as-indacenyl ligands.

[0020] The term "arenyl" ligand is used herein to mean an unsaturated cyclic hydrocarbyl ligand which may consist of one ring, or two or more fused or linked rings.

[0021] The term "monocyclic arenyl ligand" as used herein refers to a substituted or unsubstituted monoanionic C5-C6 ligand containing an aromatic five-membered single hydrocarbyl ring structure (also called a cyclopentadienyl ring). 100 Used to mean hydrocarbyl ligands.

[0022] The term "polycyclic arenyl ligand" as used herein refers to a substituted or unsubstituted monoanionic C9-C10 ligand containing an aromatic five-membered hydrocarbyl ring (also called a cyclopentadienyl ring) fused to one or two partially unsaturated or aromatic hydrocarbyl ring structures which may be fused to additional saturated, partially unsaturated or aromatic hydrocarbyl rings. 103 Used to mean hydrocarbyl ligands. The arenyl ligands may be unsubstituted or substituted. Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl), a reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, tert-butyl, and cyclobutyl). The term "vinyl" refers to an olefin having the formula: [ka] wherein R is a hydrocarbyl group, for example a saturated hydrocarbyl group, such as an alkyl group. The term "vinylidene" refers to an olefin having the formula: [ka] In the formula, R 1 and R 2 are each independently a hydrocarbyl group, for example a saturated hydrocarbyl group, such as an alkyl group.

[0023] The term "vinylene" or "1,2-di-substituted vinylene" means (i) an olefin having the formula: [ka] (ii) an olefin having the formula: [ka] (iii) A mixture of (i) and (ii) in any proportion. where R 1 and R 2 are each independently a hydrocarbyl group, for example a saturated hydrocarbyl group, such as an alkyl group.

[0024] The term "trisubstituted vinylene" refers to an olefin having the formula: [ka] In the formula, R 1 , R 2 , and R 3 are each independently a hydrocarbyl group, for example a saturated hydrocarbyl group, such as an alkyl group. The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring atoms and a tetrahydrofuran has five ring atoms. A heterocycle is a ring having a heteroatom within the ring structure, as opposed to a heteroatom-substituted ring, in which a hydrogen atom on a ring atom is replaced with a heteroatom. For example, tetrahydrofuran is a heterocycle, and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles include pyridine, imidazole, and thiazole.

[0025] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, Mz is z-average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also known as polydispersity (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol. The terms "catalyst compound," "catalyst complex," "transition metal complex," "transition metal compound," "catalyst precursor compound," and "catalyst precursor complex" are used interchangeably.

[0026] A "catalyst system" is a combination of at least one catalyst compound, at least one activator, an optional activating cofactor, and an optional support material. When "catalyst system" is used to describe such a pair prior to activation, it refers to the unactivated catalyst complex (catalyst precursor) with an activator and, optionally, an activating cofactor. When used to describe such a pair after activation, it refers to the activated complex and activator or other charge-balancing moiety. The catalyst compound may be neutral, as in the case of a catalyst precursor, or may be a charged species with a counterion, as in the case of an activated catalyst system. For purposes of this disclosure and claims thereof, when a catalyst system is described as including the neutral stable forms of the components, those skilled in the art will fully understand that the ionic forms of the components are the forms that react with monomers to produce polymers. A polymerization catalyst system is a catalyst system capable of polymerizing monomers into polymers. Furthermore, catalyst compounds and activators represented by formulas herein are intended to encompass both the neutral and ionic forms of the catalyst compounds and activators.

[0027] An "anionic ligand" is a negatively charged ligand that donates one or more electron pairs to a metal ion. A "Lewis base" or "neutral donor ligand" is a neutrally charged ligand that donates one or more electron pairs to a metal ion. Examples of Lewis bases include ethyl ether, trimethylamine, pyridine, tetrahydrofuran, dimethyl sulfide, and triphenylphosphine. The term "heterocyclic Lewis base" refers to a Lewis base that is also a heterocycle. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan. A scavenger is a compound that can be added to promote polymerization by removing impurities. Some scavengers can also act as activators and can be called coactivators. Coactivators that are not scavengers can also be used in conjunction with an activator to form an active catalyst. In at least one embodiment, the coactivator can be premixed with the transition metal compound to form an alkylated transition metal compound.

[0028] The term "continuous" refers to a system that operates without interruption or cessation for extended periods of time. For example, a continuous process for producing a polymer is one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

[0029] Solution polymerization refers to a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer or a blend thereof. Solution polymerization may be homogeneous. Homogeneous polymerization is polymerization in which the polymer product is dissolved in the polymerization medium. Suitable systems may not be turbid, as described in J. Vladimir Oliveira, C. Dariva and JC Pinto, Ind. Eng. Chem. Res., 2000, Vol. 29, p. 4627. Bulk polymerization refers to a polymerization process in which little or no inert solvent is used as a solvent or diluent, and the monomer and / or comonomer being polymerized is used as the solvent or diluent. Trace amounts of inert solvent may be used as catalyst carriers and scavengers. A bulk polymerization system contains less than 25% by weight, for example less than 10% by weight, for example less than 1% by weight, for example 0% by weight, of inert solvent or diluent.

[0030] The term "single catalyst compound" refers to a catalyst compound corresponding to a single structural formula, although such catalyst compounds may include and be used as mixtures of isomers, e.g., stereoisomers. A catalyst system utilizing a single catalyst compound refers to a catalyst system prepared using only a single catalyst compound in the preparation of the catalyst system. Therefore, such a catalyst system is distinguished from a "binary" catalyst system, which is prepared using, for example, two catalyst compounds having different structural formulas, e.g., different atom connectivity, number of atoms, and / or type of atoms in the two catalyst compounds. Thus, one catalyst compound is considered different from another catalyst compound if at least one atom differs by either number, type, or connectivity. For example, bisindenyl zirconium dichloride is different from (indenyl)(2-methylindenyl)zirconium dichloride, which is different from (indenyl)(2-methylindenyl)hafnium dichloride. Catalyst compounds that differ only in that they are stereoisomers of each other are not considered different catalyst compounds. For example, rac-dimethylsilylbis(2-methyl4-phenyl)hafnium dimethyl and meso-dimethylsilylbis(2-methyl4-phenyl)hafnium dimethyl are considered not different from each other. The terms "cocatalyst" and "activator" are used interchangeably herein and are defined as any compound capable of activating any one of the above-mentioned catalyst compounds by converting the neutral catalyst compound into a catalytically active catalyst compound cation.

[0031] Noncoordinating anion (NCA) refers to an anion that does not coordinate to the catalyst metal cation or that coordinates only weakly to the metal cation. The term NCA is also defined to include multi-component NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, which contains an acidic cationic group and a noncoordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with the catalyst to form an activated species by abstraction of the anionic group. NCAs coordinate weakly enough so that neutral Lewis bases, such as olefinically or acetylenically unsaturated monomers, can displace them from the catalytic center. Any metal or metalloid capable of forming a suitable weakly coordinating complex can be used or contained in the noncoordinating 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. The term non-coordinating anionic activators includes neutral activators, ionic activators, and Lewis acid activators. The terms "non-coordinating anionic activators" and "ionizing activators" are used interchangeably herein.

[0032] The terms "process" and "method" are used interchangeably. Additional definitions and conventions may be found below in other parts of this disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0033] The present disclosure relates to metallocene catalyst compounds, catalyst systems containing such compounds, and their uses. The inventors have discovered that metallocene catalyst compounds having a ferrocene moiety at the 4-position of the indenyl ligand can provide isotactic polypropylene and ethylene copolymers with high activity. The polymers formed can have one or more of high molecular weight, high comonomer incorporation, high melting temperature, narrow polydispersity index, and / or (in the case of polypropylene) isotacticity. Ethylene copolymers formed using the catalysts of the present disclosure can have high molecular weight and high comonomer incorporation, which can improve the processability of the formed ethylene copolymer while maintaining most, if not all, of the mechanical property advantages provided by high molecular weight.

[0034] Interestingly, isotactic polypropylene can be obtained by the embodiments described herein. Furthermore, high activity of the catalyst of the present disclosure can be obtained even when the ferrocenyl substituent is located on the six-membered indenyl ring, compared to the ferrocenyl substituent located on the five-membered indenyl ring, which is the ring closer to the catalyst metal atom. Without being bound by theory, the increased or maintained catalytic activity of the catalyst compound of the present disclosure may be realized because the ferrocenyl substituent located on the six-membered indenyl ring provides reduced steric bulk around the catalyst metal atom, compared to the ferrocenyl substituent located on the five-membered indenyl ring, which is closer to the catalyst metal atom.

[0035] The inventors have further discovered that the iron atom of the catalyst compounds of the present disclosure can be oxidized from the Fe(II) oxidation state to the Fe(III) oxidation state by forming the catalyst compound using an oxidizing agent. Similarly, the catalyst compound can be formed by reduction from the Fe(III) oxidation state to the Fe(II) oxidation state using a reducing agent. The various oxidation states of the iron in the catalyst compounds of the present disclosure provide tunable and controllable polymer properties for polymers formed using the catalysts of the present disclosure.

[0036] catalyst compound The present disclosure relates to metallocene catalyst compounds represented by formula (I): [ka] During the ceremony, M is a metal from Groups 3 to 5 of the Periodic Table, a lanthanide metal atom, or an actinide metal atom; E is a substituted polycyclic arenyl ligand bonded (e.g., π-bonded) to M and substituted with at least one ferrocenyl substituent attached to a six-membered aromatic ring of the polycyclic arenyl ligand; A is a monoanionic ligand bound to M; T is a bridging group that bonds to A and E and contains a Group 13, 14, 15, or 16 element, and is present when n is 1 and absent when n is zero; n is 0 or 1; each X is independently a monoanionic ligand, or two Xs are joined together to form a metallocycle ring when attached to M, or two Xs are joined together to form a chelating, diene, or alkylidene ligand; each L is independently a Lewis base, or two L's are joined together and attached to M to form a bidentate Lewis base; X may be joined to L to form a monoanionic bidentate group; y is 1, 2 or 3; w is 0, 1, or 2; y+w is less than or equal to 4.

[0037] In some embodiments, at least one ferrocenyl substituent of formula (I) is represented by formula (Ia): [ka] where Fe is Fe(II) or Fe(III), and R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27, and R 28 Each of R is independently hydrogen, hydrocarbyl, or any adjacent R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 may be joined to form one or more hydrocarbyl or heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, such as substituted or unsubstituted indenyl or fluorenyl, and the dashed line indicates the bond of E in formula (I) to the polycyclic arenyl ligand; n' is the charge on Fe, where n' is zero when Fe is Fe(II) and +1 when Fe is Fe(III); Y, when present, is a coordinating or non-coordinating anion (preferably non-coordinating) having a charge of −1, and is present when q is 1 and n′ is +1, and is absent when q is 0 and n′ is 0. In some embodiments, Fe in Formula (Ia) is preferably Fe(II), n′=0 (e.g., a neutral Fe center), and q is 0 (i.e., Y is absent). In some embodiments, when n′=+1, Fe in Formula (Ia) is Fe(III) (e.g., a cationic Fe center), q is 1, and Y is present. Non-limiting examples of counteranions Y include halide (e.g., chloride), tetrakis(3,5-bis(trifluoromethyl)phenylborate), tetrafluoroborate, antimony hexafluoride, phosphorus hexafluoride, tetrakis(perfluorophenylborate), and tetraphenylborate.

[0038] In some embodiments, E in Formula (I) is selected from substituted indenyl, fluorenyl, cyclopenta[b]naphthalenyl, cyclopenta[a]naphthalenyl, tetrahydro-s-indacenyl, or tetrahydro-as-indacenyl. In some embodiments, the ferrocenyl substituent in Formula (I) is located at the 4-position of the indenyl, fluorenyl, cyclopenta[b]naphthalenyl, cyclopenta[a]naphthalenyl, tetrahydro-s-indacenyl, or tetrahydro-as-indacenyl. In some embodiments, the ferrocenyl substituent in Formula (I) is located at the 5-position of the indenyl, cyclopenta[a]naphthalenyl, or tetrahydro-as-indacenyl. In some embodiments, the ferrocenyl substituent in Formula (I) is located at the 4-position of the indenyl, cyclopenta[b]naphthalenyl, or tetrahydro-s-indacenyl, such as indenyl. In some embodiments, A in formula (I) is a monocyclic or polycyclic arenyl ligand bonded (e.g., π-bonded) to M, for example, A is substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, cyclopenta[b]naphthalenyl, cyclopenta[a]naphthalenyl, tetrahydro-s-indacenyl, or tetrahydro-as-indacenyl. When A is a substituted polycyclic arenyl ligand, A can be the same as E.

[0039] Alternatively, A can be expressed as m-1-n where J is a heteroatom from Group 15 of the Periodic Table of the Elements having a coordination number of 3 or a heteroatom from Group 16 having a coordination number of 2; each R″ is independently a substituted or unsubstituted hydrocarbyl, n is 0 or 1 and indicates the presence (n=1) or absence (n=0) of a bridging group T, and m is the coordination number of the heteroatom J such that “m-1-n” indicates the number of R″ substituents attached to J.

[0040] In some embodiments, each X may independently be hydrogen, hydrocarbyl, or both X may be joined to bond to the metal atom to form a metallocycle ring containing from about 3 to about 20 carbon atoms; or both may together be an olefin, diolefin, aryne, or alkylidene ligand. In some embodiments, each X may independently be a halogen, hydride, alkoxide, sulfide, aryloxide, amide, phosphide, or other monovalent anionic ligand, or both X may be joined to form a divalent anionic chelating ligand.

[0041] In some embodiments, T of formula (I) is a bridging group that connects A and E and includes at least one Group 13, 14, 15, or 16 element, such as boron or a Group 14, 15, or 16 element. An example of a suitable bridging group is P(=S)R * , P(=Se)R * , P(=O)R * , R * 2C, R * 2Si, R * 2Ge, R * 2CCR * 2. R * 2CCR * 2CR * 2. R * 2CCR * 2CR * 2CR * 2. R * C=CR * , R * C=CR * CR * 2. R * 2CCR * =CR * CR * 2. R * C=CR * CR * =CR * , R * C=CR * CR * 2CR * 2. R * 2CSiR * 2. R * 2SiSiR *2、R * 2SiOSiR * 2、R * 2CSiR * 2CR * 2、R * 2SiCR * 2SiR * 2、R * C=CR * SiR * 2、R * 2CGeR * 2、R * 2GeGeR * 2、R * 2CGeR * 2CR * 2、R * 2GeCR * 2GeR * 2、R * 2SiGeR * 2、R * C=CR * GeR * 2、R * B、R * 2C-BR * 、R * 2C-BR * -CR * 2、R * 2C-O-CR * 2、R * 2CR * 2C-O-CR * 2CR * 2、R * 2C-O-CR * 2CR * 2、R * 2C-O-CR * =CR * 、R * 2C-S-CR * 2、R * 2CR * 2C-S-CR * 2CR * 2、R * 2C-S-CR * 2CR * 2、R * 2C-S-CR * =CR * 、R * 2C-Se-CR * 2、R* 2CR * 2C-Se-CR * 2CR * 2. R * 2C-Se-CR * 2CR * 2. R * 2C-Se-CR * =CR * , R * 2C-N=CR * , R * 2C-NR * -CR * 2. R * 2C-NR * -CR * 2CR * 2. R * 2C-NR * -CR * =CR * , R * 2CR * 2C-NR * -CR * 2CR * 2. R * 2C-P=CR * , R * 2C-PR * -CR * 2, O, S, Se, Te, NR * , PR * , AsR * , SbR * ,OO,SS,R * N-NR * , R * P-PR * , OS, O-NR * , O-PR * , S-NR * , S-PR * , and R * NPR * wherein R * is hydrogen or C1-C 20 is a hydrocarbyl, halocarbyl, silylcarbyl, or germylcarbyl substituent, and two or more adjacent R *may be linked to form a saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent. Some examples of bridging groups T include CH, CHCH, SiMe, SiPh, SiMePh, Si(CH), Si(CH), O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, MeSiOSiMe, and PBu.

[0042] In some embodiments, each occurrence of L in Formula (I) is independently selected from an ether, an amine, a phosphine, a thioether, and an ester. In some embodiments of Formula (I), L is selected from EtO, MeOtBu, EtN, PhNMe, MePhN, tetrahydrofuran, methyl acetate, and dimethyl sulfide, and each occurrence of X is independently selected from methyl, benzyl, trimethylsilyl, methylene(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydride, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamide, diethylamide, dipropylamide, and diisopropylamide.

[0043] In some embodiments, the metallocene catalyst compound of Formula (I) is represented by Formula (IIa), Formula (IIb), Formula (IIIa), Formula (IIIb), Formula (IVa), or Formula (IVb). [ka] During the ceremony, M, T, L, X, y, w, J, R″, and m are as described above for Formula (I) and / or Formula (Ia); R in formula (IIa), formula (IIb), formula (IIIa), formula (IIIb), formula (IVa), and formula (IVb) 4 , R 5 , R 6 and R 7 is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a heteroatom or heteroatom-containing group, or a ferrocenyl substituent, with the proviso that R 4 , R 5 , R 6 or R7 At least one of the R is a ferrocenyl substituent. Any adjacent R that is not ferrocenyl 4 , R 5 , R 6 , and R 7 may be joined to form one or more substituted hydrocarbyl or heterocyclic rings each having 5, 6, 7, or 8 ring atoms; R in formula (IIa) and formula (IIb) 10 , R 11 , R 12 and R 13 is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a heteroatom or heteroatom-containing group, or a ferrocenyl substituent, and any adjacent R is not ferrocenyl. 10 , R 11 , R 12 and R 13 may be joined to form one or more substituted or unsubstituted hydrocarbyl or heterocyclic rings each having 5, 6, 7, or 8 ring atoms; R of formula (IIa), formula (IIb), formula (IIIa), formula (IIIb), formula (IVa), and / or formula (IVb) 1 , R 2 , R 3 , R 8 , R 9 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 each (when present) is independently hydrogen, substituted or unsubstituted hydrocarbyl, a heteroatom, or a heteroatom-containing group, and any two adjacent R 1 , R 2 , R 3 , R 8 , R 9 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 may be joined to form one or more substituted or unsubstituted hydrocarbyl or heterocyclic rings each having 5, 6, 7, or 8 ring atoms.

[0044] In some embodiments of Formula (I), Formula (IIa), Formula (IIb), Formula (IIIa), Formula (IIIb), Formula (IVa), or Formula (IVb), M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf), such as Zr or Hf. In some embodiments of Formula (I), Formula (IIa), Formula (IIb), Formula (IIIa), Formula (IIIb), Formula (IVa), or Formula (IVb), y is 2. In some embodiments of Formula (IIa), Formula (IIb), Formula (IIIa), or Formula (IIIb), M is Zr or Hf and y is 2. In some embodiments of Formula (IVa) or Formula (IVb), M is Ti and y is 1 or 2, for example, y is 2. In some embodiments of Formula (I), Formula (IIa), Formula (IIb), Formula (IIIa), Formula (IIIb), Formula (IVa), or Formula (IVb), R 4 or R 5 In some embodiments of Formula (I), Formula (IIa), Formula (IIb), Formula (IIIa), Formula (IIIb), Formula (IVa), or Formula (IVb), R 4 is ferrocenyl.

[0045] In some embodiments of Formula (IIa) or Formula (IIb), R 4 or R 5 and R 10 or R 11 is ferrocenyl. In some embodiments of Formula (IIa) or Formula (IIb), R 4 and R 10 Each of is ferrocenyl. In some embodiments of Formula (IIa) or Formula (IIb), R 4 and R 10 one or both of R is ferrocenyl; 2 and R 8 Each of the C1-C 10 In some embodiments, R 2 and R 8is independently methyl, ethyl, propyl, or butyl. In some embodiments of Formula (IIa) or Formula (IIb), R 4 and R 10 is ferrocenyl and R 2 , R 6 , R 8 and R 12 Each of the C1-C 10 hydrocarbyl (e.g., methyl, ethyl, propyl, or butyl), and R 5 and R 11 Each of the C1-C 10 It is hydrocarbyl or alkoxy (eg methoxy). In some embodiments of Formula (IIa) or Formula (IIb), R 4 and R 10 is ferrocenyl and R 2 and R 8 Each of the C1-C 10 hydrocarbyl (e.g., methyl, ethyl, propyl, or butyl), and R 5 , R 6 , R 11 , and R 12 Each of the C1-C 10 hydrocarbyl (e.g., methyl, ethyl, propyl, or butyl), and R 5 and R 6 and / or R 11 and R 12 may be joined to form a hydrocarbyl or heterocyclic ring having 5, 6, 7, or 8 ring atoms (eg, 5 or 6 ring atoms), respectively.

[0046] In some embodiments of Formula (IIIa) or Formula (IIIb), R 4 or R 5 is ferrocenyl and R 15 , R 16 , R 17 , R 18 , and R 19 each independently represents hydrogen or C-C 10 It is hydrocarbyl (eg methyl). In some embodiments of Formula (IIIa) or Formula (IIIb), R 4 is ferrocenyl and R 15 , R 16 , R 17 , R 18 , and R 19 each independently represents hydrogen or C-C 10 is hydrocarbyl (e.g., methyl), and R 5 and R 6 Each of the C1-C 10 They may be hydrocarbyls or may be joined to form hydrocarbyl or heterocyclic rings having 5, 6, 7, or 8 ring atoms (eg, 5 or 6 ring atoms), respectively. In some embodiments of Formula (IIIa) or Formula (IIIb), R 4 is ferrocenyl and R 2 and R 6 Each of the C1-C 10 hydrocarbyl (e.g., methyl, ethyl, propyl, or butyl), and R 5 is C1-C 10 It may be a hydrocarbyl, a heteroatom, or a heteroatom-containing group (eg, alkoxy, such as methoxy).

[0047] In some embodiments of Formula (IVa) or Formula (IVb), R 4 is ferrocenyl, J is nitrogen or oxygen (preferably nitrogen), and each occurrence of R″ is independently C-C 30 Hydrocarbyl, e.g., C4-C 20 Hydrocarbyl, for example tert-butyl, neopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, adamantan-1-yl, adamantan-2-yl, norborn-1-yl, norborn-2-yl, benzyl, or ethylphenyl, for example tert-butyl, cyclododecyl or adamantan-1-yl. In some embodiments of Formula (IVa) or Formula (IVb), R 4 is ferrocenyl and R 2 and R 6Each of the C1-C 10 hydrocarbyl (e.g., methyl, ethyl, propyl, or butyl), and R 5 is C1-C 10 is a hydrocarbyl, a heteroatom, or a heteroatom-containing group (e.g., alkoxy, e.g., methoxy); J is nitrogen or oxygen (preferably nitrogen); and each occurrence of R″ is independently C-C 30 Hydrocarbyl, e.g., C4-C 20 Hydrocarbyl, for example tert-butyl, neopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, adamantan-1-yl, adamantan-2-yl, norborn-1-yl, norborn-2-yl, benzyl, or ethylphenyl, for example tert-butyl, cyclododecyl or adamantan-1-yl. In some embodiments of Formula (IVa) or Formula (IVb), R 4 is ferrocenyl and R 2 , R 5 and R 6 Each of the C1-C 10 is hydrocarbyl, and R 5 and R 6 may be joined to form a hydrocarbyl or heterocyclic ring having 5, 6, 7, or 8 ring atoms (e.g., 5 or 6 ring atoms), respectively; J is nitrogen or oxygen (e.g., nitrogen); and each occurrence of R″ is independently C-C 30 Hydrocarbyl, e.g., C4-C 20 Hydrocarbyl, for example tert-butyl, neopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, adamantan-1-yl, adamantan-2-yl, norborn-1-yl, norborn-2-yl, benzyl, or ethylphenyl, for example tert-butyl, cyclododecyl or adamantan-1-yl.

[0048] In some embodiments of Formula (IIa), Formula (IIIa), or Formula (IVa), T is a group represented by the formula (R'''2G) g’wherein each occurrence of G is independently C, Si, or Ge; g is 1 or 2; and each occurrence of R'" is independently hydrogen, halogen, or C1-C 20 and two or more R''' may form a ring structure, including an aromatic, partially saturated, or saturated cyclic or fused ring system. In some embodiments of Formula (IIa), Formula (IIIa), or Formula (IVa), T is selected from CH2, CH2CH2, C(CH3)2, CPh2, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, or Si(CH2)5. In some embodiments of Formula (I), Formula (IIa), Formula (IIb), Formula (IIIa), Formula (IIIb), Formula (IVa), or Formula (IVb), each occurrence of X can be independently selected from methyl, benzyl, trimethylsilyl, methylene(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydride, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamide, diethylamide, dipropylamide, and diisopropylamide. In at least one embodiment of any of the above formulas, each occurrence of X is independently chloro, benzyl, or methyl.

[0049] In some embodiments of any of the above formulas, w is 0, y is 2, and each occurrence of X is independently chloro, benzyl, or methyl. In some embodiments, C1-C 10 Hydrocarbyl is C1-C 10 It may also be alkyl.

[0050] In some embodiments of Formula (I), Formula (IIa), Formula (IIb), Formula (IIIa), Formula (IIIb), Formula (IVa), or Formula (IVb), each occurrence of the ferrocenyl substituent is independently represented by Formula (Ia) above, and R of Formula (Ia) 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R27 , and R 28 Each of R is independently hydrogen, hydrocarbyl, or any adjacent R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 may be joined to form one or more hydrocarbyl or heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and the dashed line indicates the bond to the catalyst compound of Formula (I), Formula (IIa), Formula (IIb), Formula (IIIa), Formula (IIIb), Formula (IVa), or Formula (IVb).

[0051] In some embodiments of Formula (I), Formula (IIa), Formula (IIb), Formula (IIIa), Formula (IIIb), Formula (IVa), or Formula (IVb), each occurrence of the ferrocenyl substituent is independently represented by Formula (Ia) above, and R of Formula (Ia) 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 is hydrogen, and the dashed line indicates a bond to a catalyst compound of Formula (I), Formula (IIa), Formula (IIb), Formula (IIIa), Formula (IIIb), Formula (IVa), or Formula (IVb). In some of the above preferred embodiments, catalysts of formula (IIa), formula (IIIa), and formula (IVa) are preferred.

[0052] In some embodiments, the catalyst compound represented by one or more of Formula (I), Formula (IIa), Formula (IIb), Formula (IIIa), Formula (IIIb), Formula (IVa), or Formula (IVb) is rac-dimethylsilanediyl-bis(η 5 -4-ferrocenyl-2-methylinden-1-yl)zirconium dichloride, rac-dimethylsilanediyl-bis(η5 -4-ferrocenyl-2-methylinden-1-yl)zirconium dimethyl, rac-dimethylsilanediyl-bis(η 5 (4-ferrocenyl-2-methylinden-1-yl)hafnium dichloride, rac-dimethylsilanediyl-bis(η 5 (4-ferrocenyl-2-methylinden-1-yl)hafnium dimethyl, rac-dimethylsilanediyl-bis(η 5 -2-butyl-4-ferrocenylinden-1-yl)zirconium dichloride, rac-dimethylsilanediyl-bis(η 5 -2-butyl-4-ferrocenylinden-1-yl)zirconium dimethyl, rac-dimethylsilanediyl-bis(η 5 -2-butyl-4-ferrocenylinden-1-yl)hafnium dichloride, rac-dimethylsilanediyl-bis(η 5 -2-butyl-4-ferrocenylinden-1-yl)hafnium dimethyl, rac-dimethylsilanediyl-bis(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)zirconium dichloride, rac-dimethylsilanediyl-bis(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)zirconium dimethyl, rac-dimethylsilanediyl-bis(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)hafnium dichloride, rac-dimethylsilanediyl-bis(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)hafnium dimethyl, rac-dimethylsilanediyl-bis(η 5-4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)zirconium dichloride, rac-dimethylsilanediyl-bis(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)zirconium dimethyl, rac-dimethylsilanediyl-bis(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)hafnium dichloride, rac-dimethylsilanediyl-bis(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)hafnium dimethyl, (dimethylsilanediyl)(η 5 -2-butyl-4-ferrocenylinden-1-yl)(κ 1 -tert-butylamido)dimethyl titanium, (dimethylsilanediyl)(η 5 -2-butyl-4-ferrocenylinden-1-yl)(κ 1 -tert-butylamido)dimethylzirconium, (dimethylsilanediyl)(η 5 -2-butyl-4-ferrocenylinden-1-yl)(κ 1 -tert-butylamido)dimethylhafnium, (dimethylsilanediyl)(η 5 -2-butyl-4-ferrocenylinden-1-yl)(κ 1 -tert-butylamido)titanium dichloride, (dimethylsilanediyl)(η 5 -2-butyl-4-ferrocenylinden-1-yl)(κ 1 -tert-butylamido)zirconium dichloride, (dimethylsilanediyl)(η 5 -2-butyl-4-ferrocenylinden-1-yl)(κ 1 -tert-butylamido)hafnium dichloride, (dimethylsilanediyl)(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 -tert-butylamido)dimethyl titanium, (dimethylsilanediyl)(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 -tert-butylamido)dimethylzirconium, (dimethylsilanediyl)(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 -tert-butylamido)dimethylhafnium, (dimethylsilanediyl)(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 -tert-butylamido)titanium dichloride, (dimethylsilanediyl)(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 -tert-butylamido)zirconium dichloride, (dimethylsilanediyl)(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 -tert-butylamido)hafnium dichloride, (dimethylsilanediyl)(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(κ 1 -tert-butylamido)dimethyl titanium, (dimethylsilanediyl)(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(κ 1-tert-butylamido)dimethylzirconium, (dimethylsilanediyl)(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(κ 1 -tert-butylamido)dimethylhafnium, (dimethylsilanediyl)(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(κ 1 -tert-butylamido)titanium dichloride, (dimethylsilanediyl)(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(κ 1 -tert-butylamido)zirconium dichloride, (dimethylsilanediyl)(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(κ 1 -tert-butylamido)hafnium dichloride, Dimethylsilanediyl(η 5 -4-ferrocenyl-2-methylinden-1-yl)(tetramethylcyclopentadienyl)zirconium dichloride, Dimethylsilanediyl(η 5 -4-ferrocenyl-2-methylinden-1-yl)(tetramethylcyclopentadienyl)zirconium dimethyl, Dimethylsilanediyl(η 5 -4-ferrocenyl-2-methylinden-1-yl)(tetramethylcyclopentadienyl)hafnium dichloride, Dimethylsilanediyl(η 5 -4-ferrocenyl-2-methylinden-1-yl)(tetramethylcyclopentadienyl)hafnium dimethyl, Dimethylsilanediyl(η 5-4-ferrocenyl-2-isopropylinden-1-yl)(tetramethylcyclopentadienyl)zirconium dichloride, Dimethylsilanediyl(η 5 -4-ferrocenyl-2-isopropylinden-1-yl)(tetramethylcyclopentadienyl)zirconium dimethyl, Dimethylsilanediyl(η 5 -4-ferrocenyl-2-isopropylinden-1-yl)(tetramethylcyclopentadienyl)hafnium dichloride, Dimethylsilanediyl(η 5 -4-ferrocenyl-2-isopropylinden-1-yl)(tetramethylcyclopentadienyl)hafnium dimethyl, Dimethylsilanediyl(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)(tetramethylcyclopentadienyl)zirconium dichloride, Dimethylsilanediyl(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)(tetramethylcyclopentadienyl)zirconium dimethyl, Dimethylsilanediyl(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)(tetramethylcyclopentadienyl)hafnium dichloride, Dimethylsilanediyl(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)(tetramethylcyclopentadienyl)hafnium dimethyl, Dimethylsilanediyl(η 5 -4-ferrocenyl-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)zirconium dichloride, Dimethylsilanediyl(η 5-4-ferrocenyl-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)zirconium dimethyl, Dimethylsilanediyl(η 5 -4-ferrocenyl-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)hafnium dichloride, Dimethylsilanediyl(η 5 -4-ferrocenyl-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)hafnium dimethyl, Dimethylsilanediyl(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)zirconium dichloride, Dimethylsilanediyl(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)zirconium dimethyl, Dimethylsilanediyl(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)hafnium dichloride, and Dimethylsilanediyl(η 5 -4-Ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)hafnium dimethyl is selected from.

[0053] In at least one embodiment, two or more different catalyst compounds are present in the catalyst system. In at least one embodiment, two or more different catalyst compounds are present in the reaction zone of the reactor in which the polymerization process of the present disclosure occurs. When two catalyst compounds are used in one reactor as a mixed catalyst system, the two catalyst compounds can be selected so that they are compatible.1 H or 13 Simple screening methods, such as C NMR, can be used to determine which catalyst compounds are suitable. The same activator can be used for both catalyst compounds, or two different activators can be used in combination, such as a non-coordinating anion activator and an alumoxane. If one or more catalyst compounds contain an X ligand that is not a hydride, hydrocarbyl, or substituted hydrocarbyl, the alumoxane can be contacted with the catalyst compounds before adding the non-coordinating anion activator.

[0054] The two or more catalyst compounds can be used in any suitable ratio. For example, the molar ratio of (A) transition metal compound to (B) transition metal compound can be (A:B) from 1:1000 to 1000:1, alternatively from 1:100 to 500:1, alternatively from 1:10 to 200:1, alternatively from 1:1 to 100:1, alternatively from 1:1 to 75:1, or alternatively from 5:1 to 50:1. The suitable ratio selected will depend on the exact catalyst compound selected, the method of activation, and the desired polymer product. In at least one embodiment, when two catalyst compounds are used and both are activated with the same activator, the molar percentages based on molecular weight of the catalyst compounds may be about 10% to about 99.9% A to about 0.1% to about 90% B; alternatively, about 25% to about 99% A to about 0.5% to about 75% B; alternatively, about 50% to about 99% A to about 1% to about 50% B; or alternatively, about 75% to about 99% A to about 1% to about 10% B.

[0055] Method for preparing catalyst compounds All air-sensitive syntheses are performed in a nitrogen-purged dry box. All solvents are available from commercial sources. A ferrocenyl substituent can be substituted onto an aryl compound, and the reaction product is then used as a ligand in the catalyst compounds of the present disclosure. To form the reaction product, the ferrocene compound is treated with a strong base, such as potassium tert-butoxide and / or butyllithium. To this mixture, a Lewis acid, such as ZnCl, is added to form an organozinc compound. A bromo-aryl compound, such as a bromo-indene compound, and a palladium catalyst, such as bis(tri-tert-butylphosphine)palladium, are introduced along with the organozinc compound to form the ferrocenyl-substituted aryl compound.

[0056] For the bridged catalyst compounds of the present disclosure, a ferrocenyl-substituted aryl compound may be treated with a strong base, such as butyllithium, and a chlorinated crosslinking compound, such as dichlorodimethylsilane, to form a dimeric ferrocenyl-substituted aryl compound bridged by the crosslinking compound. For bridged catalyst compounds of the present disclosure, a dimeric ferrocenyl-substituted aryl compound bridged by a bridging compound may be treated with a strong base, such as butyllithium, and a metal tetrachloride to form a bridged dichloro-catalyst compound of the present disclosure. Similarly, for unbridged catalyst compounds of the present disclosure, a monomeric ferrocenyl-substituted aryl compound may be treated with a strong base, such as butyllithium, and a metal tetrachloride to form an unbridged dichloro-catalyst compound of the present disclosure. Metal-alkylated embodiments of the catalyst compounds can be formed by treating the above catalyst compounds (having dichloro substitution on the catalyst metal) with an alkyl Grignard reagent or an alkyllithium reagent to form catalyst compounds with dialkyl substitution on the metal.

[0057] The inventors have further discovered that the iron atom of the catalyst compounds of the present disclosure can be oxidized from the Fe(II) oxidation state to the Fe(III) oxidation state by forming the catalyst compound using an oxidizing agent. For example, the catalyst compound described above can be treated with an oxidizing agent. Similarly, a reducing agent can be used to form the catalyst compound by reduction from the Fe(III) oxidation state to the Fe(II) oxidation state. For example, a catalyst compound containing an Fe(II) ferrocenyl substituent, as described above, can be treated with an oxidizing agent to produce a catalyst compound containing an Fe(III) ferrocenyl substituent. The Fc substituent in the Fe(III) oxidation state is cationic and has an associated counter anion to balance the charge. Cyclic voltammetry can be used to measure the half-wave potential (E 1 / 2 ) can be used to select a suitable redox agent for each complex. The various oxidation states of iron in the catalyst compounds of the present disclosure provide tunable and controllable polymer properties for polymers formed using the catalysts of the present disclosure.

[0058] oxidizing agent The oxidizing agent used to form the catalyst compounds of the present disclosure can be any suitable oxidizing agent capable of oxidizing the Fe(II) of the ferrocenyl substituent to Fe(III). In some embodiments, the oxidizing agent is selected from silver tetrakis(3,5-bis(trifluoromethyl)phenylborate, acetylferrocenium tetrakis(3,5-bis(trifluoromethyl)phenyl), nitrosonium tetrakis(3,5-bis(trifluoromethyl)phenyl), acetylferrocenium tetrafluoroborate and nitrosonium tetrafluoroborate, nitrosonium antimony hexafluoride, nitrosonium phosphorus hexafluoride, nitrosonium tetrakis(perfluorophenylborate), acetylferrocenium tetrafluoroborate, acetylferrocenium antimony hexafluoride, acetylferrocenium phosphorus hexafluoride, acetylferrocenium tetrakis(perfluorophenylborate), or combinations thereof.

[0059] reducing agent The reducing agent used to form the catalyst compounds of the present disclosure can be any suitable reducing agent capable of reducing the Fe(III) of the ferrocenyl substituent to Fe(II). In some embodiments, the reducing agent is selected from cobaltocene, bis(pentamethylcyclopentadienyl)iron, bis(pentamethylcyclopentadienyl)cobalt, sodium, potassium, lithium, acenaphthalenide, benzophenonide, or a combination thereof.

[0060] catalyst system In one or more embodiments, the catalyst system of the present disclosure includes an activator and any of the catalyst compounds described above. While the catalyst system of the present disclosure may utilize any of the catalyst compounds described above in combination with each other or with one or more catalyst compounds not described above, in some embodiments, the catalyst system utilizes a single catalyst compound corresponding to one of the catalyst compounds of the present disclosure. In yet other embodiments, the catalyst system further comprises a support material. In some embodiments, the support material is silica. In some embodiments, the activator comprises one or more of an alumoxane, an aluminum alkyl, an ionizing activator, or a combination thereof.

[0061] In another embodiment, the present disclosure relates to a method for preparing a catalyst system by contacting a catalyst compound of the present disclosure with an activator, wherein the catalyst compound is a single catalyst compound, and the single catalyst compound is the only catalyst compound contacted by the activator in the method. In yet another embodiment, the present disclosure relates to a method for polymerizing olefins, comprising contacting at least one olefin with a catalyst system and obtaining a polyolefin. In yet another embodiment, the present disclosure relates to a method for polymerizing olefins, comprising contacting two or more different olefins with a catalyst system and obtaining a polyolefin. In a further embodiment, the present disclosure relates to a catalyst system comprising the catalyst compound of any of the above-mentioned embodiments, wherein the catalyst system comprises a single catalyst compound. In a further embodiment, the present disclosure relates to a catalyst system comprising the catalyst compound of any of the above-mentioned embodiments, wherein the catalyst system consists essentially of a single catalyst compound.

[0062] activator The terms "cocatalyst" and "activator" are used interchangeably herein. The catalyst systems described herein may include the catalyst complexes described above and an activator, such as an alumoxane or a non-coordinating anion, and may be formed by combining the catalyst compounds described herein with an activator in any manner known in the literature, including combining them with a support such as silica. The catalyst systems may also be added to or generated in solution or bulk polymerizations (in monomer). The catalyst systems of the present disclosure may have one or more activators and one, two, or more catalyst components. An activator is defined as any compound capable of activating any one of the catalyst compounds described above by converting a neutral metal compound into a catalytically active metal compound cation. Non-limiting activators may include, for example, alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional cocatalysts. Suitable activators may include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract reactive σ-bonded metal ligands to cationicize the metal compounds and provide charge-balancing non-coordinating or weakly coordinating anions, such as non-coordinating anions. In at least one embodiment, the catalyst system includes an activator, a catalyst compound of Formula (I), Formula (IIa), Formula (IIb), Formula (IIIa), Formula (IIIb), Formula (IVa), or Formula (IVb), and an optional support.

[0063] Alumoxane activator Alumoxane activators are utilized as activators in the catalyst systems described herein. Alumoxanes generally have the structure -Al(R a and oligomeric compounds containing 2-O-subunits, wherein R a"'" is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, for example, when the extractable ligand is an alkyl, halide, alkoxide, or amide. Mixtures of different alumoxanes and modified alumoxanes can also be used. It may be preferable to use a visually clear methylalumoxane. Cloudy or gelled alumoxane can be filtered to produce a clear solution, or clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is modified methylalumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A and covered by U.S. Pat. No. 5,041,584, incorporated herein by reference). Another useful alumoxane is solid polymethylaluminoxane, such as those described in US Pat. No. 9,340,630, US Pat. No. 8,404,880, and US Pat. No. 8,975,209, which are incorporated herein by reference.

[0064] When the activator is an alumoxane (modified or unmodified), and in at least one embodiment, an amount of activator up to a 5,000-fold molar excess Al / M over the catalyst compound (per metal catalytic site) can be used. The minimum activator to catalyst compound can be a 1:1 molar ratio. Alternative ranges can include from about 1:1 to about 500:1, alternatively from about 1:1 to about 200:1, alternatively from about 1:1 to about 100:1, or alternatively from about 1:1 to about 50:1. In alternative embodiments, little or no alumoxane is used in the polymerization processes described herein, for example, the alumoxane may be present at zero mol %, or alternatively, the alumoxane may be present at a molar ratio of aluminum to catalyst compound transition metal of less than 500:1, such as less than 300:1, such as less than 100:1, for example less than 1:1.

[0065] Ionizing / Non-Coordinating Anionic Surfactants The term "noncoordinating anion" (NCA) refers to an anion that does not coordinate to a cation or coordinates only weakly to a cation, thereby remaining sufficiently labile to be displaced by a Lewis base. A "compatible" noncoordinating anion is one that does not degrade to neutrality upon decomposition of the initially formed complex. Furthermore, the anion does not transfer anionic substituents or fragments to the cation, resulting in the formation of a neutral transition metal compound and neutral by-products from the anion. Useful noncoordinating anions according to the present disclosure are compatible, stabilizing the transition metal cation in the sense of balancing its ionic charge to +1, while still remaining sufficiently labile to allow displacement during polymerization. Suitable ionizing activators can include NCAs, such as compatible NCAs. It is within the scope of this disclosure to use neutral or ionic ionizing activators, either alone or in combination with alumoxane or modified alumoxane activators. For a description of some suitable active agents, see US 8,658,556 and US 6,211,105, which are incorporated herein by reference. Additional suitable active agents are described in US Patent Publication No. 2021 / 0179650, which is incorporated herein by reference.

[0066] In some embodiments, the activator may be one or more of N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, dioctadecylmethylammonium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium tetra(perfluorophenyl)borate.

[0067] In at least one embodiment, the activator is selected from one or more of triarylcarbeniums (e.g., triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, or triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

[0068] Particularly useful activators are also described in PCT Application No. PCT / US2020 / 044865 (Publication No. WO2021 / 086467), U.S. Patent Application No. 16 / 394,174 (published as US2019 / 0330394), and PCT Application No. PCT / US2019 / 029056 (published as WO2019 / 210026), which include N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(pentafluorophenyl)] N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(heptafluoronaphthalenyl)borate], N-methyl-N-octadecyl-4-(octadecyloxy)anilinium [tetrakis(pentafluorophenyl)borate], N-methyl-N-octadecyl-4-(octadecyloxy)anilinium [tetrakis(heptafluoronaphthalenyl)borate], N,N-di(hydrogenated tallow)methyl The paper describes non-aromatic hydrocarbon soluble activator compounds such as N,N-di(hydrogenated tallow)methylammonium [tetrakis(heptafluoronaphthalenyl)borate], N,N-di(octadecyl)methylammonium [tetrakis(pentafluorophenyl)borate], N,N-di(octadecyl)methylammonium [tetrakis(heptafluoronaphthalenyl)borate], N,N-di(hexadecyl)methylammonium [tetrakis(pentafluorophenyl)borate], N,N-di(hexadecyl)methylammonium [tetrakis(heptafluoronaphthalenyl)borate], N-octadecyl-N-hexadecylmethylammonium [tetrakis(pentafluorophenyl)borate], and N-octadecyl-N-hexadecylmethylammonium [tetrakis(heptafluoronaphthalenyl)borate].

[0069] A suitable activator to catalyst ratio, e.g., total NCA activator to catalyst ratio, may be about a 1:1 molar ratio. Alternative ranges include about 0.1:1 to about 100:1, alternatively about 0.5:1 to about 200:1, alternatively about 1:1 to about 500:1, and alternatively about 1:1 to about 1000:1. A suitable range may be about 0.5:1 to about 10:1, e.g., about 1:1 to about 5:1.

[0070] It is also within the scope of the present disclosure that the catalyst compound can be combined with a combination of an alumoxane and an NCA (see, e.g., U.S. Pat. No. 5,153,157; ​​U.S. Pat. No. 5,453,410; EP 0573120 B1; WO 1994 / 007928; and WO 1995 / 014044, which are incorporated herein by reference, and which discuss the use of alumoxanes in combination with ionizing activators).

[0071] In the polymerization process of the present disclosure, a chain transfer agent may be used. Useful chain transfer agents may be hydrogen, alkylalumoxane, a compound represented by the formula AlR3, ZnR2 (wherein each R is independently a C1-C8 aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyloctyl, or an isomer thereof), or a combination thereof, such as diethylzinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof. Additionally, the catalyst system of the present disclosure may include a metal hydrocarbenyl chain transfer agent represented by the following formula: Al(R') 3-v (R'') v wherein each R' is independently C1-C 30 and / or each R″ may independently be a C-C hydrocarbyl group with a terminal vinyl group. 20 It may be a hydrocarbenyl group; v may be 0.1 to 3.

[0072] Any carrier material In embodiments herein, the catalyst system may include an inert support material. The support material may be a porous support material, such as talc, and inorganic oxides. Other support materials include zeolites, clays, organoclays, or other organic or inorganic support materials, or mixtures thereof.

[0073] The support material may be an inorganic oxide. The inorganic oxide may be in finely divided form. Suitable inorganic oxide materials for use in the catalyst system herein may include Group 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be used alone or in combination with silica or alumina may be magnesia, titania, and zirconia. However, other suitable support materials may be used, such as finely divided functionalized polyolefins, such as finely divided polyethylene. Examples of suitable supports may include magnesia, titania, zirconia, montmorillonite, phyllosilicates, zeolites, talc, and clay. Combinations of these support materials, such as silica-chromium, silica-alumina, and silica-titania, may also be used. In at least one embodiment, the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica clay, silicon oxide / clay, or mixtures thereof.

[0074] Carrier materials such as inorganic oxides are approximately 10 m 2 / g~about 700m 2 / g surface area, approximately 0.1 cm 3 / g ~ approx. 4.0cm 3 The support material may have a pore volume of about 5 μm to about 500 μm / g and an average particle size of about 5 μm to about 500 μm. 2 / g~about 500m 2 / g, and the pore volume may be about 0.5 cm 3 / g ~ approx. 3.5cm 3 / g and the average particle size may be from about 10 μm to about 200 μm. For example, the surface area of ​​the support material may be from about 100 m 2 / g~about 400m 2 / g, and the pore volume is about 0.8 cm 3 / g~approx.3.0cm 3 / g and the average particle size may be from about 5 μm to about 100 μm. The average pore size of the support material useful in the present disclosure may be from about 10 Å to about 1000 Å, e.g., from about 50 Å to about 500 Å, e.g., from about 75 Å to about 350 Å. In at least one embodiment, the support material is a high surface area amorphous silica (surface area=300 m 2 / gm; pore volume 1.65cm 3 / gm). For example, a suitable silica may be silica sold under the tradename DAVISON™ 952 or DAVISON™ 955 by the Davison Chemical Division of W.R. Grace and Company. In other embodiments, DAVISON™ 948 is used. Alternatively, the silica may be, for example, calcined (e.g., at 875° C.) ES-70™ silica (PQ Corporation, Malvern, Pennsylvania).

[0075] The support material should be dry, i.e., free or substantially free of absorbed water. Drying of the support material can be accomplished by heating or calcining at about 100°C to about 1000°C, e.g., at least about 600°C. When the support material is silica, it is heated to at least 200°C, e.g., about 200°C to about 850°C, e.g., about 600°C, for a period of about 1 minute to about 100 hours, about 12 hours to about 72 hours, or about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups to produce the supported catalyst system of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0076] A support material having reactive surface groups, such as hydroxyl groups, is slurried in a non-polar solvent, and the resulting slurry is contacted with a solution of a catalyst compound and an activator. In at least one embodiment, the support material slurry is first contacted with the activator for a period of about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. A solution of the catalyst compound is then contacted with the separated support / activator. In at least one embodiment, the supported catalyst system is generated in situ. In an alternative embodiment, the support material slurry is first contacted with the catalyst compound for a period of about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. The supported catalyst compound slurry is then contacted with an activator solution.

[0077] The mixture of catalyst, activator, and support is heated to about 0° C. to about 70° C., for example, about 23° C. to about 60° C., e.g., room temperature. The contact time may be about 0.5 hours to about 24 hours, for example, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. Suitable non-polar solvents are those materials in which all of the reactants used herein, such as the activator and catalyst compound, are at least partially soluble and which are liquid at the polymerization temperature. The non-polar solvent may be an alkane, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials may also be used, including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene. In at least one embodiment, the support material is supported methylalumoxane (SMAO), an MAO activator treated with silica (eg, ES-70-875 silica).

[0078] Polymerization Process The present disclosure also relates to a polymerization process in which a monomer (e.g., ethylene, propylene) and optionally a comonomer are contacted with a catalyst system comprising an activator and at least one catalyst compound of the present disclosure. The catalyst compound and activator may be combined in any suitable order. The catalyst compound and activator may be combined prior to contact with the monomer. Alternatively, the catalyst compound and activator may be introduced separately into a polymerization reactor, and the catalyst compound and activator then react to form an active catalyst. The monomer may be a substituted or unsubstituted C2-C 40 Alpha olefins, e.g., C2-C 20 Alpha olefins, e.g., C2-C 12 Alpha olefins may include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof. In at least one embodiment, the monomers are ethylene and one or more C-C 40 Olefins, e.g., C4-C 20 Olefins, e.g., C6-C 12 Contains any comonomer containing olefins. C3-C 40 The olefin monomers may be linear, branched, or cyclic. 40 The cyclic olefin may be strained or unstrained, monocyclic or polycyclic, and may contain heteroatoms and / or one or more functional groups. In another embodiment, the monomers are propylene and one or more ethylene or C4-C6 40 Olefins, e.g., C4-C 20 Olefins, e.g., C6-C 12 Includes optional comonomers including olefins. C4-C 40 The olefin monomers may be linear, branched, or cyclic. 40 Cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may contain heteroatoms and / or one or more functional groups.

[0079] Exemplary C2-C 40The olefin monomer and optional comonomer may be ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, ethylidene norbornene, vinylnorbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and their isomers, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives, such as norbornene, norbornadiene, and dicyclopentadiene.

[0080] The polymerization process of the present disclosure can be carried out in any suitable manner. Any suitable suspension, homogeneous, bulk, solution, slurry, or gas-phase polymerization process can be used. Such processes can be carried out in batch, semi-batch, or continuous mode. Homogeneous and slurry polymerization processes can be used. (A homogeneous polymerization process is defined as a process in which at least 90% by weight of the product is soluble in the reaction medium.) The homogeneous polymerization process can be a bulk homogeneous process. (A bulk process is defined as a process in which the monomer concentration in the total reactor feed is 70% by volume or greater.) Alternatively, no solvent or diluent is present or added to the reaction medium (except for minor amounts used as carriers for the catalyst system or other additives, or the amount found with the monomer, e.g., propane in propylene). In another embodiment, the process is a slurry process. As used herein, the term "slurry polymerization process" refers to a polymerization process in which a supported catalyst is used and the monomer is polymerized on the supported catalyst particles. At least 95% by weight of the polymer product obtained from the supported catalyst is in granular form as solid particles (not dissolved in the diluent).

[0081] Suitable diluents / solvents for polymerization may include non-coordinating inert liquids. Examples of diluents / solvents for polymerization include straight-chain and branched-chain 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 (e.g., Isopar®); perhalogenated hydrocarbons, such as perfluorinated C4-C 10 Alkanes, chlorobenzene, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, mesitylene, and xylene may be included. Suitable solvents may also include liquid olefins that can act 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 at least one embodiment, aliphatic hydrocarbon 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 are used as solvents. In another embodiment, the solvent is not aromatic, for example, aromatics are present in the solvent at less than 1% by weight, for example less than 0.5% by weight, for example 0% by weight, based on the weight of the solvent.

[0082] In at least one embodiment, the feed stream to the reactor has a feed concentration of monomer and comonomer for polymerization of less than 60% by volume solvent, e.g., less than 40% by volume, e.g., less than 20% by volume, based on the total volume of the feed stream. In at least one embodiment, the polymerization is carried out in a bulk process.

[0083] The polymerization can be carried out at any temperature and / or pressure suitable to obtain the desired polymer. Suitable temperatures and / or pressures include temperatures from about 0°C to about 300°C, for example, from about 20°C to about 200°C, for example, from about 35°C to about 160°C, for example, from about 80°C to about 160°C, for example, from about 85°C to about 140°C. The polymerization can be carried out at a pressure from about 0.1 MPa to about 25 MPa, for example, from about 0.45 MPa to about 6 MPa, or from about 0.5 MPa to about 4 MPa. In a preferred polymerization, the run time of the reaction may be up to about 300 minutes, e.g., from about 5 minutes to about 250 minutes, e.g., from about 10 minutes to about 120 minutes, e.g., from about 20 minutes to about 90 minutes, e.g., from about 30 minutes to about 60 minutes. In a continuous process, the run time may be the average residence time of the reactor. In at least one embodiment, the run time of the reaction is up to about 45 minutes. In a continuous process, the run time may be the average residence time of the reactor.

[0084] In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from about 0.001 psig to about 50 psig (0.007 kPa to 345 kPa), for example, from about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), for example, from about 0.1 psig to about 10 psig (0.7 kPa to 70 kPa). In at least one embodiment, the hydrogen content is from about 0.0001 ppm to about 2,000 ppm, such as from about 0.0001 ppm to about 1,500 ppm, such as from about 0.0001 ppm to about 1,000 ppm, such as from about 0.0001 ppm to about 500 ppm. Alternatively, hydrogen can be present at zero ppm. In at least one embodiment, little or no alumoxane is used in the process to produce the polymer, for example, the alumoxane may be present at zero mol %, or alternatively, the alumoxane may be present at an aluminum to transition metal molar ratio of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

[0085] Unless otherwise specified, "catalyst productivity" is a measure of how many grams of polymer (P) are produced using a polymerization catalyst containing W g of catalyst (cat) over a period of T hours, and can be represented by the formula P / (T x W), where gPgcat -1 time -1 Unless otherwise specified, "catalyst activity" is a measure of how active a catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP / molcat) or as the mass of product polymer (P) produced per mass of catalyst (cat) used (gP / gcat). Catalyst activity can also be expressed over a period of time T in hours and is reported as the mass of product polymer (P) produced per mole or millimole of catalyst (cat) used, gPmmolcat -1 time -1 It can be expressed in units of

[0086] In at least one embodiment, according to the present disclosure, the catalyst system comprises a catalyst having a mass of about 10,000 g / mmol / cat. -1 time -1 Over, for example, about 100,000gPmmolcat -1 time -1 Over, for example, about 500,000gPmmolcat -1 time -1 Ultra, for example, about 50,000gPmmolcat -1 time -1 ~Approx. 2,800,000gPmmolcat -1 time -1 , for example, about 50,000 gPmmolcat -1 time -1 ~Approx. 1,200,000gPmmolcat -1 time -1 , for example, about 200,000 gPmmolcat -1 Hour-1~about 1,000,000gPmmolcat -1 time -1 , for example, about 200,000 gPmmolcat -1 time -1 ~Approx. 500,000gPmmolcat -1 time -1, for example, about 300,000 gPmmolcat -1 time -1 ~Approx. 500,000gPmmolcat -1 time -1 , alternatively about 500,000gPmmolcat -1 time -1 ~Approx. 950,000gPmmolcat -1 time -1 , for example, about 800,000 gPmmolcat -1 time -1 ~Approx. 950,000gPmmolcat -1 time -1 It has catalytic activity of

[0087] In at least one embodiment, the polymerization is carried out 1) at a temperature of about 0°C to about 300°C (e.g., about 25°C to about 250°C, e.g., about 50°C to about 160°C, e.g., about 80°C to about 140°C); 2) at a pressure of from atmospheric pressure to about 10 MPa (e.g., from about 0.35 MPa to about 10 MPa, e.g., from about 0.45 MPa to about 6 MPa, e.g., from about 0.5 MPa to about 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, e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; e.g., when aromatics are present in the solvent at less than 1% by weight, e.g., less than 0.5% by weight, e.g., 0% by weight, based on the weight of the solvent); 4) the catalyst system used in the polymerization is 0. 0.5 mol %, e.g., about 0 mol %, of alumoxane, or alternatively, the alumoxane is present in an aluminum to transition metal molar ratio of less than 500:1, e.g., less than 300:1, e.g., less than 100:1, e.g., less than 1:1; 5) polymerization occurs in one reaction zone; 6) a scavenger (e.g., a trialkylaluminum compound) may be absent (e.g., present at zero mol %, or alternatively, the scavenger is present in an amount of less than 100:1, e.g., less than 100:1, e.g., less than 1:1); 7) hydrogen may be present in the polymerization reactor at a partial pressure of from about 0.001 psig to about 50 psig (0.007 kPa to 345 kPa), e.g., from about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), e.g., from about 0.1 psig to about 10 psig (0.7 kPa to 70 kPa). In at least one embodiment, the catalyst system used in the polymerization comprises only one catalyst compound. The "reaction zone," also referred to as the "polymerization zone," is the vessel in which the polymerization takes place, e.g., a stirred tank reactor or a loop reactor. When multiple reactors are used in a continuous polymerization process, each reactor is considered a separate polymerization zone. In the case of multiple-stage polymerization in a batch polymerization process, each polymerization stage is considered a separate polymerization zone. In at least one embodiment, polymerization occurs in one reaction zone. Room temperature is 23° C. unless otherwise specified.

[0088] Optionally, other additives may be used in the polymerization, such as one or more scavengers, hydrogen, aluminum alkyls, or chain transfer agents, such as alkylalumoxanes, compounds represented by the formula AlR or ZnR, where each R is independently a C-C aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, or an isomer thereof, or combinations thereof, such as diethylzinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof.

[0089] Polyolefin Products The present disclosure also relates to compositions of matter produced by the methods described herein. In at least one embodiment, the method described herein comprises: 20 Olefin homopolymers (e.g., ethylene homopolymers; propylene homopolymers), or C2-C 20 Olefin copolymers (e.g., ethylene-octene, ethylene-propylene, propylene-ethylene) and / or other propylene-alpha-olefin copolymers, such as C3-C 20 Copolymers (e.g., propylene-hexene or propylene-octene) are produced.

[0090] The methods of the present disclosure produce olefin polymers, such as polyethylene and propylene homopolymers and copolymers. In at least one embodiment, the polymers produced herein are homopolymers of ethylene or one or more C3-C6 olefins, e.g., from about 0.00001% to about 40% (alternatively, from about 5% to about 42%, e.g., from about 10% to about 35%, e.g., from about 10% to about 20%, alternatively, from about 20% to about 30%, e.g., from about 25% to about 30% by weight) of one or more C3-C6 olefins. 20 Olefin comonomers (e.g., C3-C 12Copolymers of ethylene with alpha-olefins such as propylene, butene, hexene, octene, decene, and dodecene (e.g., propylene, butene, hexene, and octene). For example, it has been discovered that the catalyst compounds of the present disclosure can provide ethylene copolymers with high comonomer content and provide controllable / tunable melting temperatures depending on the desired comonomer content. In at least one embodiment, the monomer is ethylene and the comonomer is hexene or octene, for example, from about 10% to about 35% hexene or octene by weight, for example, from about 10% to about 20% hexene or octene, for example, from about 15% to about 25% hexene or octene, or alternatively, from about 25% to about 33% by weight, based on the weight of the polymer.

[0091] In at least one embodiment, the polymers produced herein are homopolymers of propylene or C2 or C4-C6 propylene, e.g., from about 0.00001% to about 8% (alternatively from about 0.00001% to about 7%, e.g., from about 0.05% to about 5%, e.g., from about 0.5% to about 2.5%) by weight of propylene. 20 Olefin comonomers (e.g., ethylene or C4-C 12 Copolymers of propylene with one or more alpha-olefins, such as ethylene, butene, hexene, octene, decene, dodecene (e.g., ethylene, butene, hexene, octene). In at least one embodiment, the monomer is propylene and the comonomer is ethylene, e.g., from about 0.00001% to about 5% ethylene, e.g., from about 0.00001% to about 4% ethylene, e.g., from about 0.00001% to about 2.5% ethylene, by weight based on the weight of the polymer. In at least one embodiment, the polymers produced herein have a unimodal or multimodal molecular weight distribution as determined by gel permeation chromatography (GPC). "Unimodal" means that the GPC trace has one peak or inflection point. "Multimodal" means 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).

[0092] In at least one embodiment, the propylene homopolymer or propylene copolymer of the present disclosure has a viscosity of from about 10,000 g / mol to about 600,000 g / mol, such as from about 50,000 g / mol to about 450,000 g / mol, such as from about 100,000 g / mol to about 250,000 g / mol, such as from about 150,000 g / mol to about 225,000 g / mol, alternatively. Alternatively, it has a Mw of about 250,000 g / mol to about 500,000 g / mol, such as about 250,000 g / mol to about 450,000 g / mol, for example, about 300,000 g / mol to about 400,000 g / mol, alternatively about 50,000 g / mol to about 100,000 g / mol, alternatively about 100,000 g / mol to about 200,000 g / mol. In at least one embodiment, the propylene homopolymer or propylene copolymer of the present disclosure has a Mn of from about 1,000 g / mol to about 300,000 g / mol, such as from about 5,000 g / mol to about 250,000 g / mol, for example, from about 5,000 g / mol to about 100,000 g / mol, for example, from about 40,000 g / mol to about 85,000 g / mol, alternatively from about 100,000 g / mol to about 250,000 g / mol, for example, from about 180,000 g / mol to about 225,000 g / mol, alternatively from about 120,000 g / mol to about 170,000 g / mol.

[0093] In at least one embodiment, the propylene homopolymer or propylene copolymer of the present disclosure has a Mz of from about 100,000 g / mol to about 1,100,000 g / mol, such as from about 200,000 g / mol to about 800,000 g / mol, for example, from about 400,000 g / mol to about 800,000 g / mol, for example, from about 600,000 g / mol to about 800,000 g / mol, alternatively from about 800,000 g / mol to about 1,100,000 g / mol, alternatively from about 200,000 g / mol to about 400,000 g / mol, for example, from about 200,000 g / mol to about 300,000 g / mol, alternatively from about 100,000 g / mol to about 200,000 g / mol. In at least one embodiment, the propylene homopolymer or propylene copolymer of the present disclosure has a Mw / Mn (PDI) value of from about 1 to about 8, such as from about 1 to about 5, such as from about 1 to about 3, such as from about 1 to about 2.5, such as from about 1 to about 2.

[0094] In at least one embodiment, the propylene homopolymer or propylene copolymer of the present disclosure may have a Tm (°C) of from about 120°C to about 150°C, such as from about 122.5°C to about 150°C, for example, from about 135°C to about 147°C, for example, from about 140°C to about 145°C, alternatively from about 145°C to about 150°C, alternatively from about 130°C to about 140°C, for example, from about 130°C to about 135°C, alternatively from about 135°C to about 140°C.

[0095] The stereoregularity of isotactic propylene homopolymers and copolymers can be dictated by the catalyst, total monomer concentration, and reactor temperature. Isotactic propylene homopolymers (or copolymers) made according to the process of the present disclosure contain up to 99.99% m-divalent elements, e.g., 13 It may comprise from about 85% to about 99.99%, such as from about 90% to about 99%, for example from about 92% to about 98%, for example from about 92% to about 95%, alternatively from about 95% to about 98% mesodivalent element (m-divalent element) content (m%) as determined by C NMR, the remainder being r-divalent element content (r%).

[0096] In some embodiments, the isotactic propylene homopolymer is 13 In some embodiments, the isotactic propylene homopolymer has an [rrrr] pentavalent element content of about 0% to about 1.6%, e.g., about 0.2% to about 1.2%, e.g., about 0.3% to about 0.9%, as determined by C NMR. 13 In some embodiments, the isotactic propylene homopolymer has a [mmmm] pentavalent element content of about 80% to about 99%, for example, about 85% to about 97%, for example, about 90% to about 97%, alternatively about 80% to about 90%, for example, about 85% to about 89%, alternatively about 80% to about 85%, as determined by C NMR. 13 In some embodiments, the isotactic propylene homopolymer has an [mmmr] pentavalent element content of about 0.1% to about 10%, such as about 1% to about 10%, for example about 1% to about 5%, alternatively about 5% to about 10%, as determined by C NMR. 13 In some embodiments, the isotactic propylene homopolymer has an [rmmr] pentavalent element content of about 0.1% to about 2%, e.g., about 0.2% to about 1.1%, e.g., about 0.3% to about 0.8%, as determined by C NMR. 13 In some embodiments, the isotactic propylene homopolymer has an [mmrr] pentavalent element content of about 0.1% to about 7%, such as about 0.2% to about 4%, for example about 1% to about 3%, alternatively about 3% to about 5%, as determined by C NMR. 13 In some embodiments, the isotactic propylene homopolymer has a [mmrm+rmrr] pentavalent element content of about 0.1% to about 9%, e.g., about 0.2% to about 2%, e.g., about 0.4% to about 1%, as determined by C NMR. 13 In some embodiments, the isotactic propylene homopolymer has a [rmrm] pentavalent element content of about 0.1% to about 5%, for example, about 0.1% to about 1%, alternatively about 1% to about 2%, as determined by C NMR. 13In some embodiments, the isotactic propylene homopolymer has an [mrrr] pentavalent element content of about 0.1% to about 3%, e.g., about 0.2% to about 1%, as determined by C NMR. 13 It has an [mrrm] pentavalent element content of about 0.1% to about 4%, such as about 0.2% to about 1%, alternatively about 1% to about 2.8%, as determined by C NMR.

[0097] 13 carbon( 13 Positional defect concentration by C NMR: To measure the steric and positional defect concentration of polypropylene, 13 C NMR spectroscopy is used. 13 C NMR spectra are obtained as described in more detail below. The position defects are 13 This gives rise to multiple peaks in the carbon NMR spectrum, all of which are integrated and averaged (to the extent that they are separated from other peaks in the spectrum) to improve the accuracy of the measurement. The chemical shift offsets of the resolvable resonances used in the analysis are shown in the table below. The exact peak positions may shift as a function of the choice of NMR solvent.

[0098] [Table 1] Stereo defects, measured as "stereo defects / 10,000 monomer units," are calculated by multiplying the sum of the intensities of the mmrr, mmrm+rrmr, and rmrm resonance peaks by 5,000. The intensities used in the calculation are normalized to the total number of monomers in the sample polymer. Methods for measuring 2,1 regio defects / 10,000 monomers and 1,3 regio defects / 10,000 monomers follow standard methods. Additional references include Grassi, A. et al. Macromolecules, 1988, 21, 617-622 and Busico et al. Macromolecules, 1994, 27, pp. 7538-7543. Average mesomorphic length = 10000 / [(steric defects / 10000C) + (2,1-position defects / 10000C) + (1,3-position defects / 10000C)].

[0099] A small amount of positional defects provides a small amount of haze in an isotactic polypropylene film or eliminates the amount of haze. The isotactic polypropylene of the present disclosure may have a small amount of positional defects. In some embodiments, the polypropylene (or copolymer thereof) advantageously has less than 200 positional defects (defined as the sum of 2,1-erythro and 2,1-threo insertions and 3,1-isomerization) per 10,000 propylene units, alternatively, more than 5, 10, or 25 and less than 150, 100, or 75 positional defects per 10,000 propylene units.

[0100] In some embodiments, the propylene homopolymer or propylene copolymer advantageously has less than 125 2,1-position defects (defined as the sum of 2,1-erythro and 2,1-threo insertions) per 10,000 propylene units, for example, greater than 5, 15, or 25 and less than 75, 60, or 50 2,1-position defects per 10,000 propylene units. In some embodiments, the propylene homopolymer or propylene copolymer advantageously has less than 100 1,3-position defects (defined as 3,1 isomerization) per 10,000 propylene units, for example, greater than 5, 7, or 15 and less than 75, 55, or 40 1,3-position defects per 10,000 propylene units. In some embodiments, the propylene homopolymer or propylene copolymer has fewer than 1,100 stereodefects per 10,000 propylene units, alternatively, greater than 50, 100, or 200 stereodefects per 10,000 propylene units and fewer than 500, 400, or 350 stereodefects per 10,000 propylene units. In some embodiments, the propylene homopolymer or propylene copolymer has an average mesomorphic length of from about 20 to about 130, e.g., from about 40 to about 100, alternatively from about 20 to about 50.

[0101] In at least one embodiment, the ethylene homopolymer or ethylene copolymer of the present disclosure has a Mw of from about 10,000 g / mol to about 2,500,000 g / mol, for example, from about 200,000 g / mol to about 800,000 g / mol, for example, from about 200,000 g / mol to about 600,000 g / mol, for example, from about 250,000 g / mol to about 350,000 g / mol, alternatively from about 600,000 g / mol to about 1,500,000 g / mol, for example, from about 900,000 g / mol to about 1,300,000 g / mol, for example, from about 1,000,000 g / mol to about 1,200,000 g / mol, alternatively from about 1,200,000 g / mol to about 2,000,000 g / mol.

[0102] In at least one embodiment, the ethylene homopolymer or ethylene copolymer of the present disclosure has a Mn of from about 50,000 g / mol to about 2,000,000 g / mol, e.g., from about 100,000 g / mol to about 800,000 g / mol, e.g., from about 150,000 g / mol to about 300,000 g / mol, alternatively from about 300,000 g / mol to about 500,000 g / mol, alternatively from about 500,000 g / mol to about 850,000 g / mol, e.g., from about 550,000 g / mol to about 700,000 g / mol, e.g., from about 600,000 g / mol to about 700,000 g / mol.

[0103] In at least one embodiment, the ethylene homopolymer or ethylene copolymer of the present disclosure has a Mz of from about 200,000 g / mol to about 5,000,000 g / mol, e.g., from about 400,000 g / mol to about 1,000,000 g / mol, e.g., from about 500,000 g / mol to about 800,000 g / mol, alternatively from about 1,000,000 g / mol to about 5,000,000 g / mol, alternatively from about 2,000,000 g / mol to about 3,000,000 g / mol, alternatively from about 3,000,000 g / mol to about 4,000,000 g / mol, alternatively from about 4,000,000 g / mol to about 5,000,000 g / mol.

[0104] In at least one embodiment, the ethylene homopolymers or ethylene copolymers of the present disclosure have a Mw / Mn (PDI) value of from about 1 to about 8, such as from about 1 to about 5, for example, from about 1 to about 3, such as from about 1 to about 2.5, for example, from about 1 to about 2, alternatively from about 3 to about 5. In at least one embodiment, the ethylene homopolymer or ethylene copolymer of the present disclosure may have a Tm (°C) of from about 70°C to about 150°C, e.g., from about 100°C to about 150°C, e.g., from about 130°C to about 140°C, alternatively from about 100°C to about 115°C, alternatively from about 70°C to about 85°C.

[0105] GPC 4-D Unless otherwise specified, for purposes of the claims, the molecular weight (Mw, Mn, Mz, Mw / Mn, etc.) distributions and moments, comonomer content, and -1 ~about 3000cm -1 The chromatographic properties are determined using high-temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with a multichannel band filter-based infrared detector ensemble IR5 with a band region covering the saturated CH stretching vibrations (representing the saturated CH stretching vibrations), an 18-angle light scattering detector, and a viscometer. Three Agilent PLgel 10-μm Mixed-B LS columns are used to effect polymer separation. Reagent-grade 1,2,4-trichlorobenzene (TCB) (Sigma-Aldrich) containing approximately 300 ppm of the antioxidant BHT is used as the mobile phase at a nominal flow rate of approximately 1.0 mL / min and a nominal injection volume of approximately 200 μL. The entire system, including the transfer line, column, and detector, is housed in an oven maintained at approximately 145 °C. A given amount of sample is weighed and sealed in a standard vial to which approximately 10 μL of flow marker (heptane) is added. After loading the vial into the autosampler, the oligomer or polymer can be dissolved automatically in the instrument by adding approximately 8 mL of TCB solvent at approximately 160 °C with continuous shaking. The sample solution concentration can be approximately 0.2 to approximately 2.0 mg / mL, with lower concentrations being used for higher molecular weight samples. The concentration, c, at each point in the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal, I, using the equation c = αI, where α is the mass constant determined using polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of ​​the concentration chromatogram over the elution volume to the injected mass, which is equal to the given concentration multiplied by the injection loop volume. The conventional molecular weight (IR MW) is determined by combining a universal calibration relationship with a column calibration performed using a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 mg / mol. The MW at each elution volume is calculated according to the following equation:

number

[0106] The comonomer composition is determined by the ratio of the IR5 detector intensities corresponding to the CH2 and CH3 channels, calibrated using a series of PE and PP homo / copolymer standards whose nominal values ​​have been previously determined by NMR or FTIR. Specifically, this provides the methyls per 1000 total carbons (CH3 / 1000TC) as a function of molecular weight. The short-chain branch (SCB) content per 1000TC (SCB / 1000TC) is then calculated as a function of molecular weight by applying a chain end correction to the CH3 / 1000TC function, assuming each chain is linear and terminated with a methyl group. The mass percent comonomer is then obtained from the following formula, where f is 0.3, 0.4, 0.6, 0.8, etc. for C3, C4, C6, C8, etc. comonomers, respectively: w2=f*SCB / 1000TC The bulk composition of the polymer from GPC-IR and GPC-4D analysis is obtained by considering the total signal in the CH3 and CH2 channels between the integration limits of the concentration chromatogram. First, the following ratios are obtained:

number

[0107] The LS detector is an 18-angle Wyatt Technology High Temperature DAWN HELEOS II. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, MB, Ed.; Academic Press, 1972).

number

number

[0108] A high-temperature Agilent (or Viscotek Corporation) viscometer with four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers is used to determine the specific viscosity. One transducer measures the total pressure drop across the detector, and the other transducer, positioned between the two sides of the bridge, measures the differential pressure. The specific viscosity, ηs, of a solution flowing through the viscometer is calculated from its output. The intrinsic viscosity [η] at each point in the chromatogram is calculated from the equation [η] = ηs / c, where c is the concentration, determined from the IR5 broadband channel output. The viscosity, MW, at each point is calculated as:

number

[0109] blend In some embodiments, the polymers produced herein (e.g., polyethylene, polypropylene, or copolymers thereof) are combined with one or more additional polymers before being formed into 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, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethyl methacrylate, or any other polymer polymerizable by a high pressure free radical process. Polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resin, ethylene-propylene rubber (EPR), vulcanized EPR, ethylene-propylene-diene monomer (EPDM) polymers, block copolymers, styrenic block copolymers, polyamides, polycarbonates, polyethylene terephthalate (PET) resins, cross-linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetals, polyvinylidine fluoride, polyethylene glycol, and / or polyisobutylene.

[0110] In at least one embodiment, the polymer (e.g., polyethylene, polypropylene) is present in the blend in an amount of from about 10% to about 99% by weight, such as from about 20% to about 95% by weight, such as from about 30% to about 90% by weight, such as from about 40% to about 90% by weight, such as from about 50% to about 90% by weight, such as from about 60% to about 90% by weight, such as from about 70 to about 90% by weight, based on the weight of the polymer in the blend. Additionally, additives may be optionally included in the blend, one or more components of the blend, and / or the product formed from the blend, e.g., a film. Such additives are well known in the art and may include, for example, fillers, antioxidants (e.g., hindered phenols, such as IRGANOX™ 1010 or IRGANOX™ 1076, available from Ciba-Geigy), phosphites (e.g., IRGAFOS™ 168, available from Ciba-Geigy), antiblocking additives, tackifiers such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins, UV stabilizers, heat stabilizers, antiblocking agents, release agents, antistatic agents, pigments, colorants, dyes, waxes, silica, fillers, and talc.

[0111] film Any of the above polymers or blends thereof can be used in a variety of end uses. Such uses include, for example, monolayer or multilayer blown, extruded, and / or shrinkable films. These films can be formed by any number of well-known extrusion or coextrusion techniques, such as blown bubble film processing, in which the composition is extruded in a molten state through an annular die and then expanded to form a uniaxially or biaxially oriented melt, which is then cooled to form a tubular blown film, which is then axially cut and unfolded to form a flat film. The film can be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different degrees. One or more of the layers of the film can be oriented in the transverse and / or longitudinal directions to the same or different degrees. Uniaxial orientation can be achieved using suitable cold or hot stretching methods. Biaxial orientation can be achieved using tenter frame equipment or a double bubble process and can occur before or after the individual layers are combined. For example, an ethylene layer may be extrusion coated or laminated onto an oriented polypropylene layer, or polyethylene and polypropylene may be coextruded together as a film and then oriented. Similarly, oriented polypropylene may be laminated to oriented polyethylene, or oriented polyethylene may be coated onto polypropylene, and the combination may then be further oriented. 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 use, but a film having a thickness of about 1 μm to about 50 μm may be suitable. Films intended for packaging may have a thickness of about 10 μm to about 50 μm. The thickness of the sealing layer may be about 0.2 μm to about 50 μm. The film may have a sealing layer on both the inner and outer surfaces, or only on the inner or outer surface.

[0112] experiment The experimental methods and analytical techniques utilized in the following examples are described in this section. The chemical structures and isomers of the catalyst compounds of the present disclosure are:1 Determined by 1 H NMR. 1 H NMR data are collected using deuterated methylene chloride or deuterated benzene on a 400 MHz Bruker spectrometer with a 5 mm probe at 23 °C. Data are recorded using a maximum pulse width of 45°, 8 seconds between pulses, and signal averaging of 16 transients. Spectra are reported relative to residual protium in deuterated benzene referenced at 7.16 ppm. Room temperature is 23°C unless otherwise specified.

[0113] The synthesized catalyst precursors are shown below. [ka] [ka]

[0114] Catalyst precursor synthesis Starting Reagents : Ferrocene (abbreviated as Fc; Acros) in hexane n BuLi(Acros), in pentane tBuLi (Acros), MeLi (Aldrich) in diethyl ether, MeMgBr (Aldrich) in diethyl ether, TiCl4 (Merck), ZrCl4 (THF)2 (Aldrich), HfCl4 (Strem), AlCl3 (Merck), potassium tert-butoxide (Acros), sodium ethoxide (Acros), 2-bromobenzyl bromide (ABCR), tert-butylamine (Acros), N-methylimidazole (Acros), dichlorodimethylsilane (Merck), diethyl 2 β-Butyl malonate (Aldrich), bis(tri-tert-butylphosphine)palladium (Aldrich), Pd2dba3 (dba = dibenzylideneacetone, Aldrich), tri-tert-butylphosphine (Aldrich), SOCl2 (Acros), NaBH4 (Acros), TsOH (Ts = toluenesulfonyl, Aldrich), Na2SO4 (Merck), K2CO3 (Merck), Na2CO3 (Merck), silica gel 60 (40–63 μm) (Merck), KOH (Merck), 12 M HCl (Merck), absolute ethanol (Merck), methanol (Merck), dichloromethane (Merck) for extraction of organic products, and Celite (Aldrich) were used as supplied. THF and diethyl ether were freshly distilled over sodium benzophenone ketyl and stored over 4A molecular sieves. Toluene (Merck), benzene (Aldrich), pentane (Merck), hexane (Merck), dichloromethane (Merck), CDCl3 (Deutero GmbH) and CD2Cl2 (Deutero GmbH) for NMR experiments were stored over 4A molecular sieves. ZnCl2 (Merck) was dried under vacuum at 120 °C. 7-Bromo-2-methyl-1H-indene was prepared as described in [Izmer, VV; Lebedev, AY; Nikulin, MV; Ryabov, AN; Asachenko, AF; Lygin, AV; Sorokin, DA; Voskoboynikov, AZ Organometallics 2006, 25, pg. 1217].4-Bromo-6-(tert-butyl)-5-methoxy-2-methyl-2,3-dihydro-1H-inden-1-one was prepared as described in [Nifant'ev, IE; Ivchenko, PV; Bagrov, VV; Churakov, AV; Mercandelli, P. Organometallics 2012, 31, pp. 4962-4970]. 2,6,6-Trimethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one was prepared as described in [Canich, JAM; Atienza, CCH; Izmer, VV; Kononovich, DS; Voskoboynikov, AZ US 2016 / 0244535 A1].

[0115] Example 1 rac-dimethylsilanediyl-bis(η 5 Preparation of (4-ferrocenyl-2-methylinden-1-yl)zirconium dichloride (complex 1) 7-(Ferrocen-1-yl)-2-methyl-1H-indene [ka] To a mixture of ferrocene (26.0 g, 140 mmol) and potassium tert-butoxide (1.91 g, 17.0 mmol) in 500 ml of THF, tBuLi (1.9 M in pentane, 147 mL, 280 mmol) was added dropwise at −78° C. over 20 minutes. The resulting suspension was warmed to −20° C. and stirred at this temperature for 1 hour. ZnCl (21.0 g, 154 mmol) was then added at −78° C., and the resulting mixture was warmed to ambient temperature. 7-Bromo-2-methyl-1H-indene (29.3 g, 140 mmol) and bis(tri-tert-butylphosphine)palladium (0.15 M in toluene, 93.0 mL, 14.0 mmol) were then added to the resulting organozinc compound. The reaction mixture was refluxed overnight, cooled to ambient temperature, poured into water (1000 mL), and the crude product was extracted with dichloromethane (3×200 mL). The combined extracts were passed through a thin layer of silica gel 60 (40-63 um), and the eluate was dried over Na2SO4 and then evaporated to dryness. The residue was triturated with 300 ml of pentane, and the resulting suspension was then filtered through a glass frit (G3), and the precipitate was dried under vacuum. Yield: 42.0 g (96%) of an orange solid as a mixture of isomers. HRMS (APPI): [M+H] - C 20 H 19 Fe + Calculated: 315.0831; Found: 315.0836. 1 H NMR (400 MHz, CDCl3): δ 7.38 (d, J = 7.8 Hz, 1H), 7.22 (t, J = 7.5 Hz, 1H), 7.15 (d, J = 7.3 Hz, 1H), 6.52 (m, 1H), 4.74 - 4.72 (m, 2H), 4.35 - 4.33 (m, 2H), 4.09 (s, 5H), 3.45 (s, 2H), 2.21 (s, 3H). 1 H NMR (400 MHz, CDCl3): δ 7.44 (d, J = 7.7 Hz, 1H), 7.30 - 7.25 (m, 2H), 7.03 (br.s., 1 H), 4.66 - 4.62 (m, 2H), 4.35 - 4.32 (m, 2H), 4.14 (s, 5H), 3.35 (s, 2H), 2.22 (s, 3H). Mixture of isomers13 C NMR (101MHz, CDCl3): δ 146.3, 145.7, 145.6, 143.8, 143.1, 139.6, 133.9, 130.4, 127.1, 126.9, 126.5, 126.5, 123.4, 123.3, 121.3, 117.7, 86.4, 85.2, 69.4, 68.5, 68.4, 68.2, 67.8, 43.6, 42.7, 17.0, 16.8.

[0116] Bis(4-ferrocenyl-2-methyl-1H-inden-1-yl)dimethylsilane [ka] To a solution of 7-(ferrocen-1-yl)-2-methyl-1H-indene (22.0 g, 70.0 mmol) in 500 ml of diethyl ether, n BuLi (2.5 M in hexane, 28.0 mL, 70.0 mmol) was added slowly at −30°C. The resulting suspension was stirred overnight at ambient temperature, then cooled to −78°C, and N-methylimidazole (100 mg) was added. The resulting mixture was stirred at −78°C for 5 minutes, and then dichlorodimethylsilane (4.52 g, 35.0 mmol) was added in one portion. The mixture was stirred overnight at ambient temperature and then passed through a short pad of silica gel 60 (40-63 μm), which was further washed with dichloromethane (2 × 100 mL). The combined eluates were evaporated to dryness, and the residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane = 5:1, by volume). Yield: 15.0 g (63%) of the title product as an orange foam. NMR spectroscopy indicated that the product was a mixture of rac- and meso-isomers. HRMS (ESI): [M] + C 42 H 40 Fe2Si + Calculated value: 684.1593; Measured value: 684.1595. 1H NMR (400 MHz, CDCl3): δ 7.46 - 7.36 (4H in m, rac or meso), 7.31 - 7.25 (4H in m, meso or rac), 7.22 - 7.16 (4H in m, rac and meso), 7.11 - 7.03 (4H in m, meso and rac), 4.72 - 4.63 (8H in m, rac or meso), 4.37 - 4.33 (8H in meso or rac), 4.13 (s, 10H, in rac or meso), 4.13 (s, 10H, in meso or rac), 3.78 (4H in br. s., rac and meso), 2.31 (6H in s, rac or meso), 2.24 (6H in s, meso or rac). -0.21 (s, 3H in meso), -0.21 (s, 6H in rac), -0.24 (s, 3H in meso). 13 C NMR (101MHz, CDCl3): δ 146.9, 146.7, 145.3, 145.3, 142.5, 142.4, 130.6, 126.7, 126.6, 125.3, 125.2, 122.6, 122.6, 121.2, 121.1, 86.6, 86.5, 69.4, 68.4, 68.4, 68.4, 68.3, 47.2, 47.1, 18.2, 18.1, -5.7, -5.7, -5.8.

[0117] rac-dimethylsilanediyl-bis(η 5 (4-Ferrocenyl-2-methylinden-1-yl)zirconium dichloride (Complex 1) [ka] To a solution of bis(4-ferrocenyl-2-methyl-1H-inden-1-yl)dimethylsilane (11.9 g, 17.4 mmol) in 600 ml of diethyl ether at −40° C. nBuLi (2.5 M in hexane, 13.9 mL, 34.7 mmol) was added in one portion. The mixture was stirred overnight at ambient temperature, the resulting orange suspension was cooled to -78 °C, and ZrCl4(THF)2 (6.56 g, 17.4 mmol) was then added. The reaction mixture was stirred at room temperature for 24 h and then evaporated to dryness. The residue was heated with toluene (200 mL), and the hot suspension that formed was filtered through a short pad of Celite. The filtrate was evaporated to dryness to give a ca. 1:1 mixture of rac- and meso-complexes. The crude product was recrystallized from toluene to give the rac-complex (2.05 g, 14%) contaminated with ca. 4% meso-complex as a red-orange powder. Elemental analysis: C 42 H 38 Calculated values ​​for Cl2Fe2SiZr: C, 59.72; H, 4.53. Found values: C, 59.96; H, 4.70. For the rac complex 1 H NMR (400 MHz, CD2Cl2): δ 7.61 (d, J = 8.6 Hz, 2H), 7.47 (d, J = 7.0 Hz, 2H), 7.26 (s, 2H), 7.01 (dd, J = 8.6, 7.1 Hz, 2H), 4.77 - 4.63 (m, 4H), 4.40 - 4.27 (m, 4H), 4.11 (s, 10H), 2.28 (s, 6H), 1.34 (s, 6H). 13 C NMR (101 MHz, CD2Cl2): δ 137.4, 135.8, 132.0, 128.5, 125.9, 125.5, 123.6, 123.5, 85.3, 84.2, 70.8, 69.9, 69.7, 69.0, 66.8, 19.0, 2.7. Meso complex 1H NMR (400 MHz, CD2Cl2): δ 7.56 (d, J = 8.8 Hz, 2H), 7.25 (d, J = 7.8 Hz, 2H), 7.11 (s, 2H), 6.73 - 6.77 (m, 2H), 4.59 - 4.61 (m, 4H), 4.31 - 4.33 (m, 4H), 4.08 (s, 10H), 3.51 (s, 6H), 1.45 (s, 3H), 1.26 (s, 3H).

[0118] Example 2 rac-dimethylsilanediyl-bis(η 5 Preparation of (4-ferrocenyl-2-methylinden-1-yl)zirconium dimethyl (complex 2) [ka] rac-dimethylsilanediyl-bis(η 5 (4-Ferrocenyl-2-methylinden-1-yl)zirconium dichloride (100 mg, 0.118 mmol) was dissolved in 15 mL of benzene. To this solution was added MeLi (1.6 M in diethyl ether, 0.222 mL, 0.355 mmol), and the mixture was stirred at room temperature for 2 days. The mixture was then filtered through Celite, and the Celite was rinsed three times with 2 mL of benzene. The resulting orange filtrate was placed under vacuum and lyophilized with CH to yield a fine orange powder. This material was suspended in pentane (20 mL) and filtered to give the product as a bright orange solid (64.3 mg; 68% yield).

[0119] Example 3 rac-dimethylsilanediyl-bis(η 5 Preparation of (4-ferrocenyl-2-methylinden-1-yl)hafnium dichloride (complex 3) [ka] To a solution of bis(4-ferrocenyl-2-methyl-1H-inden-1-yl)dimethylsilane (5.00 g, 7.30 mmol) in 250 ml of diethyl ether at −40° C. nBuLi (2.5 M in hexane, 5.84 ml, 14.6 mmol) was added in one portion. The mixture was stirred overnight at ambient temperature, then the resulting orange suspension was cooled to -78 °C, and HfCl4 (2.34 g, 7.30 mmol) was added. The mixture was stirred at room temperature for 24 hours and then evaporated to dryness. The residue was heated with toluene (100 ml), and the hot suspension formed was filtered through a short pad of Celite. The filtrate was evaporated to dryness to give a ca. 1:1 mixture of rac- and meso-complexes. The crude product was recrystallized from toluene to give 0.38 g (6%) of pure rac-complex (Catalyst ID 3A) and 0.10 g (1%) of a ca. 1:8 mixture of rac / meso-complexes (Catalyst ID 3B). Rac-complex. Elemental analysis: C 42 H 38 Calculated values ​​for Cl2Fe2SiHf: C, 54.13; H, 4.11. Found values: C, 54.27; H, 4.24. 1 H NMR (400 MHz, CDCl3): δ 7.63 (d, J = 8.7 Hz, 2H), 7.50 (d, J = 7.0 Hz, 2H), 7.16 (s, 3H), 7.02 - 6.96 (m, 2H), 4.72 (br.s., 2H), 4.70 (br.s., 2H), 4.33 (br.s., 4H), 4.14 (s, 10H), 2.38 (s, 6H), 1.33 (s, 6H). 13 C NMR (101 MHz, CDCl3): δ 136.8, 132.5, 131.4, 126.3, 125.3, 125.3, 122.8, 121.3, 85.1, 84.5, 70.5, 69.6, 69.0, 68.5, 66.6, 18.6, 2.5. Meso complex. 1H NMR (600 MHz, CDCl3): δ 7.58 (d, J = 8.8 Hz, 2H), 7.21 - 7.15 (m, 2H), 7.00 (s, 2H), 6.74 (dd, J = 7.1, 8.7 Hz, 2H), 4.65 - 4.58 (m, 4H), 4.32 - 4.26 (m, 4H), 4.10 (s, 10H), 2.62 (s, 6H), 1.45 (s, 3H), 1.26 (s, 3H). 13 C NMR (151MHz, CDCl3): δ 135.5, 134.7, 134.4, 126.5, 125.0, 124.1, 124.1, 118.8, 85.9, 85.3, 70.2, 69.6, 68.6, 68.4, 67.1, 18.8, 2.8, 2.6.

[0120] Example 4 rac-dimethylsilanediyl-bis(η 5 Preparation of (2-butyl-4-ferrocenylinden-1-yl)zirconium (complex 4) 2-(2-Bromobenzyl)hexanoyl chloride [ka] To a solution of sodium ethoxide (prepared from sodium metal (10.9 g, 472 mmol) and 400 ml of absolute ethanol), diethyl 2-butylmalonate (100 g, 463 mmol) was added dropwise over 15 minutes. The mixture was stirred for 15 minutes, and then 2-bromobenzyl bromide (116 g, 463 mmol) was added dropwise. The mixture was refluxed for 4 hours and then cooled to room temperature. A solution of KOH (104 g, 1.85 mol) in 200 ml of water was then added. The mixture was refluxed for 3 hours to saponify the formed ester. Ethanol and water were distilled off. To the residue, water (500 ml) was added, followed by 12 M HCl (to pH 1). The substituted butylmalonic acid was extracted with dichloromethane (3 × 100 ml). The combined organic extracts were dried over NaSO and then evaporated to dryness. After decarboxylation of the substituted butylmalonic acid at 160°C for 2 hours, crude 2-(2-bromobenzyl)hexanoic acid was obtained. The product was used without further purification. A mixture of the obtained 2-(2-bromobenzyl)hexanoic acid and SOCl2 (100 mL, 166 g, 1.39 mol) was stirred at room temperature for 12 hours. Excess SOCl2 was removed by distillation under vacuum, and subsequent distillation of the remaining product at a boiling point of 120°C-150°C / 2 mbar gave 108 g (89%) of a yellow liquid. Elemental analysis: C 13 H 16 Calculated for BrClO: C, 51.43; H, 5.31. Found: C, 51.32; H, 5.40. 1 H NMR (400 MHz, CDCl3): δ 7.57 (d, J = 7.98 Hz, 1H), 7.28 - 7.24 (m, 2H), 7.16 - 7.10 (m, 1H), 3.33 - 3.22 (m, 1H), 3.20 - 3.12 (m, 1H), 3.04 - 3.27 (m, 1H), 1.91 - 1.79 (m, 1H), 1.73 - 1.62 (m, 1H), 1.50 - 1.29 (m, 4H), 0.92 (t, J = 7.0 Hz, 3H). 13С NMR (101 MHz, CDCl3): δ 176.3, 137.0, 133.0, 131.3, 128.6, 127.5, 124.4, 56.7, 38.0, 31.5, 28.6, 22.4, 13.7.

[0121] 4-Bromo-2-butyl-2,3-dihydro-1H-inden-1-one [ka] To a suspension of AlCl (59.3 g, 444 mmol) in 1000 ml of dichloromethane was added dropwise a solution of 2-(2-bromobenzyl)hexanoyl chloride (108 g, 355 mmol) in 50 ml of dichloromethane at 0° C. The mixture was stirred at room temperature for 20 hours and then heated at 2000 cm 3 The mixture was poured onto crushed ice. The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 x 200 ml). The combined organic extracts were washed with 10% K2CO3, dried over anhydrous K2CO3, and then passed through a short column of silica gel 60 (40-63 um). The resulting eluate was evaporated to dryness. Distillation of the residue, boiling point 138-140°C / 2 mbar, gave 70.1 g (88%) of a colorless oil. HRMS (ESI): [M+Na] + C 13 H 15 BrNaO + Calculated value: 289.0198; Measured value: 289.0191. 1 H NMR (400 MHz, CDCl3): δ 7.76 (dd, J = 0.8 Hz, 7.8 Hz, 1H), 7.70 (d, J = 7.5 Hz, 1H), 7.28 (t, J = 7.7 Hz, 1H), 3.28 (dd, J = 7.6 Hz, 17.5 Hz, 1H), 2.80 - 2.65 (m, 2H), 2.05 - 1.89 (m, 1H), 1.57 - 1.25 (m, 5H), 0.91 (t, J = 7.1 Hz, 3H). 13С NMR (101 MHz, CDCl3): δ 207.8, 153.2, 138.7, 137.1, 128.9, 122.5, 122.0, 47.2, 33.8, 30.9, 29.3, 22.5, 13.8.

[0122] 7-Bromo-2-butyl-1H-indene [ka] To a solution of 4-bromo-2-butyl-2,3-dihydro-1H-inden-1-one (62.2 g, 233 mmol) in 500 ml of THF was added NaBH4 (13.2 g, 350 mmol) at 5 °C. To the resulting suspension, 250 ml of methanol was added dropwise with vigorous stirring at 5 °C. The reaction mixture was stirred at room temperature overnight. The volatiles were evaporated, and the residue was diluted with 1000 ml of water. The crude product was extracted with dichloromethane (300 ml). The organic extract was evaporated to dryness. The residue was dissolved in 500 ml of toluene, and 1.0 g of TsOH was added. The resulting mixture was refluxed on a Dean-Stark head for 1 hour, then cooled to room temperature and washed with 10% Na2CO3. The organic layer was separated, dried over K2CO3, and passed through a short column with silica gel 60 (40-63 μm). The resulting eluate was evaporated to dryness. Distillation of the residue at bp 132-135°C / 6 mbar gave 52.6 g (90%) of a colorless oil. HRMS (ESI): [M+Na] + C 13 H 15 BrNa + Calculated value: 273.0249; Measured value: 273.0243. 1H NMR (400 MHz, CDCl3): δ 7.29 - 7.24 (m, 1H), 7.24 - 7.19 (m, 1H), 7.16 - 7.09 (m, 1H), 7.58 - 6.53 (m, 1H), 3.33 (s, 2H), 2.53 (t, J = 7.6 Hz, 2H), 1.64 (quintet, 7.6 Hz, 2H), 1.49 - 1.36 (m, 2H), 0.99 (t, J = 7.3 Hz, 3H). 13 С NMR (101 MHz, CDCl3): δ 151.5, 147.1, 143.0, 128.1, 126.5, 126.0, 118.7, 118.4, 42.6, 31.0, 30.8, 22.5, 13.9.

[0123] 2-Butyl-7-ferrocenyl-1H-indene [ka] To a mixture of ferrocene (8.19 g, 44.0 mmol) and 0.67 g (6.00 mmol) of potassium tert-butoxide in 160 ml of THF, tBuLi (1.9 M in pentane, 46.3 mL, 88.0 mmol) was added dropwise at −78°C over 20 minutes. The resulting suspension was warmed to −20°C and stirred at this temperature for 1 hour. ZnCl (6.54 g, 48.0 mmol) was then added at −78°C, and the resulting mixture was allowed to warm to ambient temperature. 7-Bromo-2-butyl-1H-indene (10.1 g, 40.0 mmol), Pddba (0.73 g, 0.80 mmol), and tri-tert-butylphosphine (0.65 g, 3.20 mmol) were subsequently added to the resulting organozinc solution. The reaction mixture was refluxed overnight, cooled to ambient temperature, and poured into water (1000 mL). The crude product was extracted with dichloromethane (3 × 200 mL). The combined organic extracts were passed through a thin layer of silica gel 60 (40-63 um). The eluate was dried over Na2SO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10:1, by volume). Yield: 11.6 g (81%) as a red solid. HRMS (APPI): [M+H] + C 23 H 25 Fe - Calculated value: 357.1300; Measured value: 357.1302. 1 H NMR (400 MHz, CDCl3): δ 7.46 - 7.42 (m, 1H), 7.31 - 7.26 (m, 1H), 7.25 - 7.20 (m, 1H), 6.61 - 6.57 (m, 1H), 4.80 - 4.75 (m, 2H), 4.41 - 4.38 (m, 2H) 4.14 (br.s., 5H), 3.51 (s, 2H), 2.59 (t, J = 7.6 Hz, 2H), 1.75 - 1.65 (m, 2H), 1.54 - 1.43 (m, 2H), 1.03 (t, J = 7.3 Hz, 3H). 13C NMR (101 MHz, CDCl3): δ 150.5, 146.1, 139.5, 133.9, 126.5, 126.0, 123.3, 117.9, 85.3, 69.4, 68.3, 67.9, 41.9, 31.2, 30.9, 22.5, 14.0.

[0124] Bis(2-butyl-4-ferrocenyl-1H-inden-1-yl)dimethylsilane [ka] To a solution of 2-butyl-7-ferrocenyl-1H-indene (8.00 g, 22.5 mmol) in 200 ml of diethyl ether, n BuLi (2.5 M in hexane, 8.98 ml, 22.5 mmol) was added slowly at -30°C. The resulting suspension was stirred overnight at ambient temperature, then the resulting solution was cooled to -78°C, and N-methylimidazole (50 mg) was added. The resulting mixture was stirred at -78°C for 5 minutes, and then dichlorodimethylsilane (1.45 g, 11.2 mmol) was added in one portion. The mixture was stirred overnight at ambient temperature and then filtered through a short pad of silica gel 60 (40-63 um), which was further washed with dichloromethane (2 x 30 ml). The combined eluates were evaporated to dryness, and the residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10:1, by volume). Yield: 7.79 g (90%) of product as an orange foam. NMR spectrum indicated that this product possessed two diastereomers. HRMS (ESI): [M] + C 48 H 52 Fe2Si + Calculated value: 768.2532; Measured value: 768.2536. 1H NMR (400 MHz, CDCl3): δ 7.48-7.40 (m, 4H in rac and meso + 2H in rac or meso), 7.35-7.29 (m, 4H in rac and meso), 7.25 (br.s, 2H in meso or rac), 7.12 (t, J = 7.5, 2H, in rac or meso), 7.11 (t, J = 7.5, 2H, in meso or rac), 4.75-4.67 (m, 8H in rac or meso), 4.42-4.36 (m, 8H in meso or rac), 4.18 (s, 10H, in rac or meso), 4.18 (s, 10H, in meso or rac), 3.87 (s, 2H, in rac or meso), 3.86 (in s, 2H, meso or rac), 2.77-2.39 (8H in m, rac and meso), 1.87-1.58 (8H in m, rac and meso), 1.54-1.36 (8H in m, rac and meso), 1.02 (t, J = 6.6 Hz, in 6H, rac or meso), 0.99 (t, J = 6.6 Hz, in 6H, meso or rac), -0.15 (in s, 3H, meso), -0.15 (in s, 6H, rac), -0.26 (in s, 3H, meso). 13 C NMR (101MHz, CDCl3): δ 152.1, 151.9, 145.2, 145.0, 142.4, 142.3, 130.6, 130.6, 125.2, 125.2, 125.0, 125.0, 122.6, 121.2, 86.6, 86.6, 77.3, 76.7, 69.3, 68.6, 68.6, 68.3, 68.2, 68.2, 68.2, 46.0, 46.0, 31.6, 31.5, 22.6, 22.6, 14.1, 14.0, -5.2, -5.2, -5.5.

[0125] rac-dimethylsilanediyl-bis(η 5-2-butyl-4-ferrocenylinden-1-yl)zirconium dichloride (complex 4) [ka] To a solution of bis(2-butyl-4-ferrocenyl-1H-inden-1-yl)dimethylsilane (3.60 g, 4.68 mmol) in 250 ml of diethyl ether cooled to -40°C, n BuLi (2.5 M in hexane, 3.75 ml, 9.37 mmol) was added in one portion. The mixture was stirred at ambient temperature overnight. The resulting orange suspension was cooled to -78 °C, and ZrCl4(THF)2 (1.77 g, 4.68 mmol) was added. The reaction mixture was warmed to ambient temperature, stirred for 24 h, and then evaporated to dryness. The residue was heated with toluene (100 ml), and the hot suspension that formed was filtered through a short pad of Celite. The filtrate was evaporated to dryness to give an approximately 1:1 mixture of rac- and meso-complexes. The crude product was recrystallized from toluene to give 0.73 g (17%) of the rac-complex and 0.60 g (14%) of the rac-complex contaminated with 5% meso-complex as a dark red crystalline solid. Rac-complex. Elemental analysis: C 48 H 50 Calculated values ​​for Cl2Fe2SiZr: C, 62.07; H, 5.43. Found values: C, 62.25; H, 5.60. 1 H NMR (400 MHz, CDCl3): δ 7.59 (d, J = 8.7 Hz, 2H), 7.49 (d, J = 7.0 Hz, 2H), 7.32 (s, 2H), 7.01 (dd, J = 7.1, 8.6 Hz, 2H), 4.81 - 4.73 (m, 2H), 4.70 (m, 2H), 4.38 - 4.31 (m, 4H), 4.14 (s, 10H), 2.83 - 2.73 (m, 2H), 2.49 - 2.33 (m, 2H), 1.53 (m, 4H), 1.37 - 1.24 (m, 4H), 1.34 (s, 6H), 0.89 (t, J = 7.3 Hz, 6H). 13C NMR (101 MHz, CDCl3): δ 141.0, 137.3, 131.9, 127.9, 125.5, 125.2, 123.0, 121.6, 85.1, 82.7, 70.7, 69.5, 69.3, 68.5, 66.4, 35.1, 32.5, 22.4, 13.9, 3.3.

[0126] Example 5 rac-dimethylsilanediyl-bis(η 5 Preparation of (2-butyl-4-ferrocenylinden-1-yl)hafnium dichloride (complex 5) [ka] To a solution of bis(2-butyl-4-ferrocenyl-1H-inden-1-yl)dimethylsilane (3.70 g, 4.81 mmol) in 200 ml of diethyl ether at −40° C. n BuLi (2.5 M in hexane, 3.85 mL, 9.63 mmol) was added in one portion. The mixture was stirred overnight at ambient temperature, and the resulting orange suspension was cooled to −78° C., and HfCl (1.54 g, 4.81 mmol) was added. The reaction mixture was stirred at room temperature for 24 h and then evaporated to dryness. The residue was heated with toluene (100 mL), and the hot suspension that formed was filtered through a short pad of Celite. The filtrate was evaporated to dryness to give a ca. 1:1 mixture of rac- and meso-complexes. The crude product was recrystallized from toluene to give a crop of pure rac-complex (0.17 g, 3%) (catalyst ID 5A) and rac / meso mixtures (0.06 g, 83% meso, 1% yield; 0.41 g, 84% rac, 8% yield; 1.03 g, 68% meso-complex (catalyst ID 5B), 21% yield) as pale orange crystalline solids. Rac-complex. Elemental analysis: C 48 H 50 Calculated values ​​for Cl2Fe2HfSi: C, 56.74; H, 4.96. Found values: C, 56.93; H, 5.15. 11H NMR (400 MHz, CDCl3): δ 7.64 (d, J = 8.7 Hz, 2H), 7.47 (d, J = 7.0 Hz, 2H), 7.23 (s, 2H), 6.99 (dd, J = 7.1, 8.7 Hz, 2H), 4.78 - 4.73 (m, 2H), 4.71 - 4.66 (m, 2H), 4.34 (s, 4H), 4.13 (s, 10H), 2.93 - 2.82 (m, 2H), 2.52 - 2.41 (m, 2H), 1.57 - 1.46 (m, 四氢), 1.37 - 1.23 (m, 四氢), 1.33 (s, 6H), 0.89 (t, J = 7.3 Hz, 6H). Regarding rac 13 13C NMR (101 MHz, CDCl3): δ138.3, 136.8, 131.4, 126.3, 125.2, 125.0, 123.0, 119.7, 85.2, 83.7, 70.6, 69.5, 69.2, 68.5, 66.3, 35.4, 32.4, 22.5, 13.9, 3.2. Meso complex. 1 1H NMR (400 MHz, CDCl3): δ 7.59 (d, J = 8.7 Hz, 2H), 7.22 (d, J = 6.8 Hz, 2H), 7.06 (s, 2H), 6.72 (dd, J = 7.2, 8.6 Hz, 2H), 4.65 - 4.56 (m, 4H), 4.29 (br. S., 4H), 4.09 (s, 10H), 2.92 (t, J = 7.2 Hz, 4H), 1.69 - 1.53 (m, 4H), 1.46 (s, 3H), 1.41 - 1.31 (m, 4H), 1.23 (s, 3 H), 0.92 (t, J = 7.3 Hz, 6 H). 13 13C NMR (101MHz, CDCl3): δ 140.3, 135.6, 134.2, 126.7, 124.7, 124.2, 124.1, 117.5, 85.3, 85.1, 70.3, 69.5, 68.8, 68.3, 66.7, 35.9, 35.4, 32.8, 22.6, 13.9, 3.5, 3.1.

[0127] Example 6 rac-dimethylsilanediyl-bis(η 5 Preparation of (6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)zirconium dichloride (complex 6) 7-Bromo-5-tert-butyl-6-methoxy-2-methyl-1H-indene [ka] To a solution of 4-bromo-6-(tert-butyl)-5-methoxy-2-methyl-2,3-dihydro-1H-inden-1-one (16.6 g, 53.2 mmol) in 100 ml of THF was added NaBH4 (3.02 g, 79.8 mmol) at 5 °C. To the resulting suspension, 50 ml of methanol was added dropwise at 5 °C, and the reaction mixture was stirred at room temperature overnight and then evaporated to dryness. The residue was diluted with 1 L of water, and the crude product was extracted with dichloromethane (3 × 100 ml). The organic extract was evaporated to dryness. The residue was dissolved in 500 ml of toluene, and 0.06 g of TsOH was added. The resulting mixture was refluxed on a Dean-Stark head for 1 hour, then cooled to room temperature and washed with 10% Na2CO3. The organic layer was separated, dried over K2CO3, passed through a short column with silica gel 60 (40-63 um), and the eluate thus obtained was evaporated to dryness. Yield: 12.5 g (80%) of a colorless oil. HRMS (ESI): [M+Na] + C 15 H 19 BrNaO + Calculated value: 317.0511; Measured value: 317.0516. 1 H NMR (400MHz, CDCl3): δ 7.18 (s, 1H), 6.47 - 6.45 (m, 1H), 3.96 (s, 3H), 3.28 (s, 2H), 2.16 (s, 3H), 1.44 (s, 9H). 13 C NMR (101MHz, CDCl3): δ 153.1, 145.7, 143.3, 143.0, 141.6, 126.9, 117.2, 114.5, 77.3, 76.7, 61.9, 44.8, 35.4, 31.1, 16.6.

[0128] 5-tert-butyl-7-ferrocenyl-6-methoxy-2-methyl-1H-indene [ka] To a mixture of ferrocene (8.00 g, 43.0 mmol) and potassium tert-butoxide (0.58 g, 5.20 mmol) in 400 ml of THF, t BuLi (1.8 M in pentane, 47.8 mL, 88.0 mmol) was added dropwise over 20 minutes at −78°C. The resulting suspension was warmed to −20°C and stirred at this temperature for 1 hour. ZnCl (6.45 g, 47.3 mmol) was then added at −78°C, and the resulting mixture was allowed to warm to ambient temperature. 7-Bromo-5-tert-butyl-6-methoxy-2-methyl-1H-indene (11.5 g, 39.1 mmol), Pddba (0.72 g, 0.78 mmol), and tri(tert-butyl)phosphine (0.63 g, 3.13 mmol) were subsequently added to the resulting organozinc compound. The reaction mixture was refluxed overnight, cooled to ambient temperature, poured into water (1000 mL), and the crude product was extracted with dichloromethane (3 × 200 mL). The combined organic extracts were passed through a thin layer of silica gel 60 (40-63 um), dried over Na2SO4, and the eluate was evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10:1, by volume). Yield: 10.0 g (64%) as a red solid. HRMS (APPI): [M+H] - C 25 H 29 FeO + Calculated value: 401.1562; Measured value: 401.1563. 1H NMR (400 MHz, CDCl3): δ 7.21 (s, 1H), 6.53 - 6.44 (m, 1H), 4.93 (br. s., 2H), 4.42 - 4.39 (m, 2H), 4.12 (s, 5H), 3.72 (s, 2H), 3.34 (s, 3H), 2.27 (s, 3H), 1.50 (s, 9H). 13 C NMR (101 MHz, CDCl3): δ 155.9, 144.2, 141.1, 141.0, 140.6, 127.1, 126.7, 116.5, 83.2, 69.8, 69.2, 67.5, 60.8, 44.4, 35.1, 31.1, 16.7.

[0129] Bis(6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)dimethylsilane [ka] To a solution of 5-tert-butyl-7-ferrocenyl-6-methoxy-2-methyl-1H-indene (7.00 g, 17.5 mmol) in 200 ml of diethyl ether, n BuLi (2.5 M in hexane, 6.99 ml, 17.5 mmol) was added slowly at −30°C. The formed suspension was stirred overnight at ambient temperature, then cooled to −78°C, and 50 mg of N-methylimidazole was added. The resulting mixture was stirred at −78°C for 5 minutes, followed by the addition of dichlorodimethylsilane (1.13 g, 8.74 mmol) in one portion. The resulting mixture was stirred overnight at ambient temperature and then filtered through a short pad of silica gel 60 (40-63 um), which was further washed with dichloromethane (2 × 30 ml). The combined filtrates were evaporated to dryness, and the residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10:1, by volume). Yield: 4.23 g (56%) of the title product as an orange foam. NMR spectroscopy indicated that the product was a ca. 1:3 mixture of two diastereomers. HRMS (ESI): [M] + C52 H 60 Fe2O2Si + Calculated value: 856.3056; Measured value: 856.3052. 1 H NMR (400 MHz, CDCl3): δ 7.61 (4H in s, rac and meso), 7.46 (2H in s, rac), 7.33 (2H in s, meso), 4.79 - 4.68 (8H in m, rac or meso), 4.41 - 4.36 (8H in m, meso or rac), 4.20 (10H in s, rac), 4.19 (10H in s, meso), 3.73 (2H in s, rac), 3.67 (2H in s, meso), 3.26 (6H in s, rac), 3.25 (6H in s, meso), 2.37 (6H in s, rac), 2.35 (6H in s, meso), 1.45 (18H in s, meso), 1.44 (s, rac), -0.09 (s, 3H in meso), -0.10 (s, 3H in meso), -0.16 (s, 6H in rac). 13 C NMR (101 MHz, CDCl3): δ 156.9, 146.1, 143.1, 139.7, 139.7, 137.4, 137.3, 128.0, 127.9, 123.0, 123.0, 120.1, 120.0, 83.7, 83.7, 70.8, 70.7, 69.3, 67.5, 67.3, 60.5, 46.6, 35.1, 31.4, 31.4, 18.4, 18.2, -5.0, -5.2, -5.7.

[0130] rac-dimethylsilanediyl-bis(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)zirconium dichloride (complex 6) [ka] To a solution of bis(6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)dimethylsilane (2.00 g, 2.33 mmol) in 250 ml of diethyl ether cooled to -40°C, n BuLi (2.5 M in hexane, 1.87 ml, 4.67 mmol) was added in one portion. The mixture was stirred overnight at ambient temperature, the resulting orange suspension was cooled to -78 °C, and ZrCl4(THF)2 (0.88 g, 2.33 mmol) was added. The reaction mixture was warmed to ambient temperature, stirred at this temperature for 24 h, and then evaporated to dryness. The residue was triturated with 50 ml of toluene, and the hot suspension that formed was filtered through a short pad of Celite. The filtrate was evaporated to dryness to give a ca. 2:1 mixture of the rac- and meso-complexes. The crude product was recrystallized from toluene to give the pure rac-complex (0.40 g, 17%) as a dark red crystalline solid. Elemental analysis: C 52 H 58 Calculated values ​​for Cl2Fe2O2SiZr: C, 61.42; H, 5.75. Found values: C, 61.65; H, 8.82. 1 H NMR (400 MHz, CDCl3): δ 7.58 (s, 2H), 7.49 (s, 2H), 4.87 (br. s., 2H), 4.71 (br. s., 2H), 4.34 (br. s., 2H), 4.31 (br. s., 2H), 4.03 (s, 10H), 3.45 (s, 6H), 2.28 (s, 6H), 1.40 (s, 18H), 1.34 (s, 6H). Regarding rac 13 C NMR (101MHz, CDCl3): δ 161.0, 144.2, 134.3, 132.2, 124.9, 123.7, 123.2, 119.9, 82.1, 81.4, 71.8, 69.4, 69.3, 68.7, 67.5, 63.0, 35.7, 30.5, 18.6, 2.4.

[0131] Example 7 rac-dimethylsilanediyl-bis(η5 Preparation of (6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)hafnium dichloride (complex 7) [ka] To a solution of bis(6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)dimethylsilane (1.84 g, 2.15 mmol) in 200 ml of diethyl ether cooled to -40°C, n BuLi (2.5 M in hexane, 1.72 ml, 4.30 mmol) was added in one portion. The mixture was stirred overnight at ambient temperature. To the resulting orange suspension, cooled to -78°C, was added HfCl4 (0.69 g, 2.15 mmol). The mixture was stirred for 24 hours and then evaporated to dryness. The residue was triturated with 50 ml of toluene, and the hot suspension that formed was filtered through a short pad of Celite. The filtrate was evaporated to dryness to give a ca. 2:1 mixture of the rac- and meso-complexes. The crude product was recrystallized from toluene to give the pure rac-complex (0.21 g, 9%) as a pale orange crystalline solid. Elemental analysis: C 52 H 58 Calculated for Cl2Fe2HfO2: C, 56.56; H, 5.29. Found: C, 56.77; H, 5.40. 1 H NMR (400 MHz, CDCl3): δ 7.54 (s, 2H), 7.47 (s, 2H), 4.88 (br. s., 2H), 4.68 (br. s., 2H), 4.34 (br. s., 2H), 4.31 (br. s., 2H), 4.03 (s, 10H), 3.44 (s, 6H), 2.36 (s, 6H), 1.41 (s, 18H), 1.33 (s, 6H). 13 C NMR (101MHz, CDCl3): δ 161.0, 144.2, 134.3, 132.2, 124.9, 123.7, 123.2, 119.9, 82.1, 81.4, 71.8, 69.4, 69.3, 68.7, 67.5, 63.0, 35.7, 30.5, 18.6, 2.4.

[0132] Example 8 rac-dimethylsilanediyl-bis(η 5 Preparation of (4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)zirconium dichloride (complex 8) 4-Bromo-2,6,6-trimethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one [ka] To a suspension of AlCl (21.8 g, 164 mmol) in 200 mL of dichloromethane was added dropwise a solution of 2,6,6-trimethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one (14.0 g, 65.5 mmol) in 50 mL of dichloromethane at 0 °C. Next, a solution of bromine (3.3 mL, 10.5 g, 65.5 mmol) in 20 mL of dichloromethane was added dropwise at 0 °C for 1 h. The resulting mixture was poured into a solution of HCl (1 M, 500 mL) cooled to 0 °C, and the crude product was extracted with dichloromethane (3 × 100 mL). The combined organic extracts were dried over Na SO and evaporated to dryness. The residue was recrystallized from hexane at −20 °C to give 13.4 g (69%) of the title product as a yellow solid. HRMS (ESI): [M+Na] + C 15 H 17 BrNaO + Calculated value: 315.0355; Measured value: 315.0352. 1 H NMR (400 MHz, CDCl3): δ 7.43 (s, 1H), 3.25 (dd, J = 7.8 Hz, 17.4 Hz, 1H), 2.82 (s, 2H), 2.78 (s, 2H), 2.76 - 2.66 (m, 1H), 2.56 (dd, J = 3.3 Hz, 17.4 Hz, 1H), 1.29 (d, J = 7.6 Hz, 3H), 1.15 (s, 6H). 13 C NMR (101 MHz, CDCl3): δ 208.2, 151.9, 151.8, 145.1, 137.1, 119.1, 118.4, 48.8, 47.9, 42.3, 39.9, 35.6, 28.5, 16.3.

[0133] 4-Bromo-2,2,6-trimethyl-1,2,3,5-tetrahydro-s-indacene [ka] To a solution of 4-bromo-2,6,6-trimethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one (10.6 g, 36.0 mmol) in 100 ml of THF was added NaBH4 (2.00 g, 54.0 mmol) at 5 °C. To the resulting suspension, 50 ml of methanol was added dropwise at 5 °C. The reaction mixture was stirred overnight at room temperature, then evaporated to dryness, and the residue was diluted with 1 L of water. The substituted alcohol was extracted with dichloromethane (2 × 100 ml). The organic extract was evaporated to dryness. The residue was dissolved in 500 ml of toluene, and 0.05 g of TsOH was added. The mixture thus obtained was refluxed on a Dean-Stark head for 1 hour, then cooled to room temperature, and washed with 10% Na2CO3. The organic layer was separated, dried over K2CO3, passed through a short column with silica gel 60 (40-63 um), and the resulting eluate was evaporated to dryness. The residue was distilled at 110 °C / 1 mbar using a Kugelrohr apparatus. Yield: 8.1 g (81%) of a yellow solid. HRMS (ESI): [M+Na] + C 15 H 17 BrNa + Calculated value: 299.0406; Measured value: 299.0401. 1 H NMR (400MHz, CDCl3): δ 6.98 (s, 1H), 6.50 - 6.41 (m, 1H), 3.26 - 3.21 (m, 2H), 2.82 (s, 2H), 2.78 (s, 2H), 2.15 (s, 3H), 1.18 (s, 6H). 13 С NMR (101 MHz, CDCl3): δ 145.7, 145.5, 143.3, 141.2, 138.7, 127.1, 116.3, 115.2, 48.7, 48.3, 43.8, 39.6, 28.9, 16.7.

[0134] 4-Ferrocenyl-2,2,6-trimethyl-1,2,3,5-tetrahydro-s-indacene [ka] To a mixture of ferrocene (10.0 g, 53.8 mmol) and potassium tert-butoxide (0.72 g, 6.45 mmol) in 500 ml of THF, t BuLi (1.9 M in pentane, 56.6 mL, 108 mmol) was added dropwise at −78°C over 20 minutes. The resulting suspension was warmed to −20°C and stirred at this temperature for 1 hour. ZnCl (8.06 g, 59.1 mmol) was then added at −78°C, and the resulting mixture was allowed to warm to ambient temperature. 4-Bromo-2,2,6-trimethyl-1,2,3,5-tetrahydro-s-indacene (13.6 g, 48.9 mmol), Pddba (0.90 g, 0.98 mmol), and tri(tert-butyl)phosphine (0.79 g, 3.91 mmol) were subsequently added to the resulting organozinc compound. The reaction mixture was refluxed overnight, cooled to ambient temperature, poured into water (1000 mL), and the crude product was extracted with dichloromethane (3 × 200 mL). The combined organic extracts were passed through a thin layer of silica gel 60 (40-63 um), and the eluate was dried over Na2SO4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10:1, by volume). Yield: 15.2 g (81%) as a red solid. HRMS (APPI): [M+H] + C 25 H 27 Fe - Calculated value: 383.1457; Measured value: 383.1452. 1H NMR (400 MHz, CDCl3): δ 7.07 (s, 1H), 6.59 - 6.43 (m, 1H), 4.75 (t, J = 1.8 Hz, 2H), 4.46 - 4.32 (m, 2H), 4.17 (s, 5H), 3.53 (s, 2H), 3.14 (s, 2H), 2.82 (s, 2H), 2.23 (s, 3H), 1.27 (s, 6H). 13 C NMR (101MHz, CDCl3): δ 145.1, 144.6, 142.8, 138.8, 137.0, 130.4, 126.9, 114.8, 85.2, 69.1, 69.0, 67.7, 49.1, 47.5, 44.4, 40.0, 28.9, 16.7.

[0135] Bis(4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilane [ka] To a solution of 4-ferrocenyl-2,2,6-trimethyl-1,2,3,5-tetrahydro-s-indacene (10.0 g, 26.2 mmol) in 300 ml of diethyl ether, nBuLi (2.5 M in hexane, 10.5 ml, 26.2 mmol) was added slowly at −30°C. The resulting suspension was stirred overnight at ambient temperature, then cooled to −78°C, and 50 ml of N-methylimidazole was added. The resulting mixture was stirred at −78°C for 5 minutes, and then dichlorodimethylsilane (1.69 g, 13.1 mmol) was added in one portion. The mixture was further stirred overnight at ambient temperature and then filtered through a short pad of silica gel 60 (40-63 um), which was further washed with dichloromethane (2 × 30 ml). The combined filtrates were evaporated to dryness, and the residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10:1, by volume). Yield: 4.63 g (43%) of the title product as a red solid. NMR spectroscopy shows that the product is a mixture of two diastereomers in a ratio of approximately 1.1 to 1, with the rac-compound predominating. HRMS (ESI): [M] + C 52 H 56 Fe2Si + Calculated value: 820.2845; Measured value: 820.2847. 1H NMR (400 MHz, CDCl3): δ 7.51 (br. s., 4H in rac and meso), 7.24 (s., 2H in rac), 7.17 (s., 2H in meso), 4.71-4.63 (m., 8H in rac or meso), 4.39 (br. s., 8H in meso or rac), 4.20 (s., 10H in rac or meso), 4.20 (s., 10H in meso or rac), 3.77 (s., 2H in meso), 3.75 (s., 2H in rac), 3.06-2.69 (m., 16H in rac and meso), 2.37 (s., 6H in meso), 2.33 (s., 6H in rac), 1.26 (s., 6H in rac), 1.24 (s, 6H in meso), 1.14 (s, 6H in rac), 1.13 (s, 6H in meso), -0.09 (s, 3H in meso), -0.13 (s, 6H in rac), -0.14 (s, 3H in meso). 13 C NMR (101MHz, CDCl3): δ 144.8, 144.6, 144.1, 141.5, 141.5, 139.0, 138.9, 138.7, 127.8, 127.7, 126.5, 118.3, 118.3, 85.8, 85.8, 70.2, 70.1, 69.5, 69.4, 69.2, 67.6, 67.6, 67.4, 67.3, 48.8, 48.7, 47.9, 47.8, 46.6, 46.5, 40.1, 40.1, 29.0, 28.9, 28.9, 28.8, 18.3, -5.4, -5.4, -5.4.

[0136] rac-dimethylsilanediyl-bis(η 5 (4-Ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)zirconium dichloride (Complex 8) [ka] To a solution of bis(4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilane (3.00 g, 3.66 mmol) in 250 ml of diethyl ether cooled to -40°C, n BuLi (2.5 M in hexane, 2.92 ml, 7.31 mmol) was added in one portion. The mixture was stirred at ambient temperature overnight. The resulting orange solution was cooled to -78 °C, and ZrCl4(THF)2 (1.38 g, 3.66 mmol) was added. The resulting mixture was warmed to ambient temperature, stirred at this temperature for 24 h, and evaporated to dryness. The residue was heated with 50 ml of toluene, and the hot suspension formed was filtered through a short pad of Celite. The filtrate was evaporated to dryness to give a ca. 1:1 mixture of the rac- and meso-complexes. The crude product was recrystallized from toluene to give the pure rac-complex (0.35 g, 10%) (Catalyst ID 8A) and another crop of pure meso-complex (0.09 g, 3%) (Catalyst ID 8B), both as dark red crystalline solids. Rac-complex. Elemental analysis: C 52 H 54 Calculated values ​​for Cl2Fe2SiZr: C, 63.67; H, 5.55. Found values: C, 63.82; H, 5.68. 1 H NMR (400 MHz, CDCl3): δ 7.46 (s, 2H), 7.36 (s, 2H), 4.77 (br. s., 4H), 4.36 (br. s., 2H), 4.30 (br. s., 2H), 4.14 (s, 10H), 3.18 - 3.03 (m, 2H), 3.02 - 2.90 (m, 2H), 2.91 - 2.80 (m, 2H), 2.56 (m, 2H), 2.29 (s, 6H), 1.32 (br. s., 12H), 1.10 (s, 6H). 13C NMR (101 MHz, CDCl3): δ 144.3, 141.6, 133.3, 132.0, 130.6, 127.8, 124.0, 117.3, 84.1, 81.8, 77.3, 76.7, 71.5, 69.3, 68.7, 68.0, 67.8, 48.0, 47.7, 40.3, 28.8, 28.3, 18.5, 2.8. Meso complex. Elemental analysis: C 52 H 54 Calculated values ​​for Cl2Fe2SiZr: C, 63.67; H, 5.55. Found values: C, 63.85; H, 5.62. 1 H NMR (400 MHz, CDCl3): δ 7.29 (s, 2H), 7.22 (s, 2H), 4.67 (br. s., 2H), 4.59 (br. s., 2H), 4.34 (br. s., 2H), 4.29 (br. s., 2H), 4.13 (s, 10H), 2.97 - 2.81 (m, 4H), 2.73 - 2.43 (m, 4H), 2.46 (s, 6H), 1.42 (s, 3H), 1.21 (s, 3H), 1.16 (s, 6H), 0.98 (s, 6H).

[0137] Example 9 rac-dimethylsilanediyl-bis(η 5 Preparation of (4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)hafnium dichloride (complex 9) [ka] To a solution of bis(6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)dimethylsilane (3.42 g, 4.17 mmol) in 200 ml of diethyl ether cooled to -40°C, nBuLi (2.5 M in hexane, 3.33 ml, 8.33 mmol) was added in one portion. The mixture was stirred at ambient temperature overnight. The resulting orange solution was cooled to -78°C, and HfCl4 (1.34 g, 4.17 mmol) was added. The reaction mixture was stirred at ambient temperature for 24 hours and then evaporated to dryness. The residue was heated with 50 ml of toluene, and the hot suspension that formed was filtered through a short pad of Celite. The filtrate was evaporated to dryness to give a ca. 2:1 mixture of the rac- and meso-complexes. The crude product was recrystallized from toluene to give the pure rac-complex (0.59 g, 13%) as a pale orange crystalline solid. Elemental analysis: C 52 H 54 Calculated values ​​for Cl2Fe2HfSi: C, 58.47; H, 5.10. Found values: C, 58.63; H, 5.26. 1 H NMR (400 MHz, CDCl3): δ 7.39 (s, 2H), 7.35 (s, 2H), 4.74 (br. s., 4H), 4.35 (br. s., 2H), 4.28 (br. s., 2H), 4.12 (s, 10H), 3.15 - 2.94 (m, 4H), 2.93 - 2.54 (m, 4H), 2.37 (s, 6H), 1.32 (s, 6H), 1.31 (s, 6H), 1.08 (s, 6H). 13 C NMR (101 MHz, CDCl3): δ 144.0, 141.5, 131.4, 130.6, 130.1, 126.1, 122.1, 117.3, 84.2, 82.9, 71.4, 69.3, 68.7, 68.0, 67.7, 48.0, 47.6, 40.4, 28.7, 28.3, 18.4, 2.8.

[0138] Example 10 (dimethylsilanediyl)(η 5 -2-butyl-4-ferrocenylinden-1-yl)(κ 1 Preparation of (tert-butylamido)dimethyltitanium (complex 10) (2-butyl-4-ferrocenyl-1H-inden-1-yl)chlorodimethylsilane [ka] To a solution of 2-butyl-7-ferrocenyl-1H-indene (3.41 g, 9.57 mmol) in 70 ml of THF, n BuLi (2.5 M in hexane, 3.83 ml, 9.57 mmol) was added at −78° C. The resulting mixture was warmed to ambient temperature and stirred at this temperature for 1 h. The mixture was then cooled to −78° C., and dichlorodimethylsilane (6.17 g, 47.9 mmol) was added in one portion. The resulting solution was stirred at room temperature overnight, then evaporated to dryness, the residue was dissolved in hot toluene, and the resulting mixture was filtered through a short pad of Celite. The filtrate was evaporated to dryness to afford 3.90 g (91%) of the title product as a dark brown viscous oil, which was used further without additional purification. 1 H NMR (400 MHz, CDCl3): δ 7.41 (d, J = 7.6 Hz, 1H), 7.37 (d, J = 7.5 Hz, 1H), 7.26 (s, 1H), 7.09 (t, J = 7.6 Hz, 1H), 4.68 (br. s., 2H), 4.37 (s, 2H), 4.14 (s, 5H), 3.73 (s, 1H), 2.81 - 2.60 (m, 2H), 1.85 - 1.59 (m, 2H), 1.53 - 1.36 (m, 2H), 1.00 (t, J = 7.3 Hz, 3H), 0.45 (s, 3H), 0.18 (s, 3H). 13 C NMR (101 MHz, CDCl3): δ 150.7, 142.8, 142.3, 130.8, 125.8, 125.8, 122.9, 121.6, 86.5, 77.3, 76.7, 69.4, 68.5, 68.4, 68.4, 68.3, 48.5, 31.5, 31.3, 22.6, 14.0, 1.2, -0.6.

[0139] (N-tert-butylamido)(2-butyl-4-ferrocenyl-1H-inden-1-yl)dimethylsilane (A) and (N-tert-butylamido)(2-butyl-7-ferrocenyl-1H-inden-3-yl)dimethylsilane (B) [ka] To a solution of tert-butylamine (0.16 g, 2.23 mmol) in 15 ml of diethyl ether, n BuLi (2.5 M in hexane, 0.89 ml, 2.23 mmol) was added slowly at −30° C. and stirred at this temperature for 2 hours. Then, a solution of (2-butyl-4-ferrocenyl-1H-inden-1-yl)chlorodimethylsilane (1.00 g, 2.23 mmol) in 10 ml of diethyl ether was added dropwise at −30° C. The resulting mixture was stirred for 12 hours and then evaporated to dryness. The residue was dissolved in hot toluene, and the resulting suspension was filtered through a short pad of Celite. The filtrate was evaporated to dryness to give 0.95 g (88%) of the target material as a 3:1 mixture of isomers A and B as a dark red viscous oil, which was used further without additional purification. HRMS (ESI): [M+H] + C 29 H 40 FeNSi + Calculated value: 486.2274; Measured value: 486.2271. 1H NMR (400 MHz, CDCl3): δ 7.64 (dd, J = 0.9, 7.6 Hz, 1H in B), 7.44 (dd, J = 0.9, 7.7 Hz, 1H in B), 7.39 (t, J = 6.8 Hz, 1H in A), 7.32 - 7.26 (m, 1H in B), 7.22 (s, 1H in A), 7.08 (t, J = 7.6 Hz, 1H in A), 4.77 - 4.69 (m, 4H in A or B), 4.40 - 4.35 (m, 4H in A or B), 4.17 (s, 5H in A), 4.15 (s, 5H in B), 3.57 (s, 2H in B), 3.56 (s, 2H in A), 2.85 - 2.55 (m, 4H in A and B), 1.85 - 1.61 (m, 4H and B), 1.57 - 1.41 (m, 4H in A and B), 1.24 (s, 9H in A), 1.24 (s, 9H in B), 1.04 (t, J = 7.4 Hz, 3H in A), 1.03 (t, J = 7.3 Hz, 3H in B), 0.86 (br. s, 1H in B), 0.65 (br. s, 1H in A), 0.56 (s, 6H in B), 0.20 (s, 3H in A), 0.04 (s, 3H in A). 13 C NMR (101 MHz, CDCl3): δ 160.8, 153.0, 150.4, 145.5, 142.2, 140.0, 136.1, 133.5, 130.0, 126.1, 124.6, 123.7, 123.2, 122.0, 121.3, 120.4, 86.9, 86.0, 69.4, 69.3, 68.4, 68.2, 68.1, 68.1, 49.8, 49.5, 44.3, 33.7, 33.6, 33.2, 31.7, 31.6, 23.1, 22.7, 14.1, 14.1, 4.1, 0.9, -0.4.

[0140] (dimethylsilanediyl)(η 5-2-butyl-4-ferrocenylinden-1-yl)(κ 1 -tert-butylamido)dimethyltitanium (complex 10) [ka] To a solution of the above mixture of (N-tert-butylamido)(2-butyl-4-ferrocenyl-1H-inden-1-yl)dimethylsilane and (N-tert-butylamido)(2-butyl-7-ferrocenyl-1H-inden-3-yl)dimethylsilane (0.81 g, 1.67 mmol) in 20 mL of diethyl ether, MeLi (1.6 M in diethyl ether, 5.20 mL, 8.34 mmol) was added dropwise at 0 °C. The resulting mixture was stirred at ambient temperature for 2 hours. Then, a solution of TiCl (0.18 mL, 0.32 g, 1.67 mmol) in 2 mL of hexane was added in one portion. The resulting mixture was stirred overnight and then evaporated to dryness. To the residue was added MeMgBr (2.9 M in diethyl ether, 1.72 mL, 5.00 mmol) and 100 mL of hexane. The mixture thus obtained was stirred overnight at ambient temperature, then filtered through a short pad of Celite, and the filtrate obtained was evaporated to dryness. The crude product was recrystallized from pentane at -30°C. Yield: 0.45 g (48%) of a dark brown solid. Elemental analysis: C 31 H 43 Calculated values ​​for FeNSiTi: C, 66.31; H, 7.72; N, 2.49. Found values: C, 66.18; H, 7.73; N, 2.63. 1H NMR (400 MHz, CDCl3): δ 7.59 (s, 1 H), 7.42 (d, J = 7.5 Hz, 2 H), 7.08 - 7.00 (m, 1 H), 4.82 - 4.77 (m, 1 H), 4.76 - 4.71 (m, 1 H), 4.45 - 4.38 (m, 2 H), 4.20 (s, 5 H), 2.59 - 2.50 (m, 1 H), 2.43 (dd, J = 7.1, 15.3 Hz, 1 H), 1.75 - 1.63 (m, 3 H), 1.57 - 1.50 (m, 9 H), 1.47 - 1.37 (m, 3 H), 0.94 (t, J = 7.3 Hz, 4 H), 0.72 (s, 3 H), 0.64 (s, 3 H), 0.63 (s, 3 H), -0.44 (s, 3 H). 13 C NMR (101 MHz, CDCl3): δ 146.9, 136.2, 135.1, 129.5, 125.0, 124.8, 123.9, 115.0, 88.2, 85.7, 69.6, 69.5, 69.5, 69.5, 69.4, 69.4, 69.4, 68.9, 68.4, 66.6, 58.1, 56.6, 50.9, 34.2, 34.0, 32.3, 22.6, 14.0, 6.3, 5.6.

[0141] Example 11 (dimethylsilanediyl)(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 Preparation of (tert-butylamido)dimethyltitanium (complex 11) (6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)chlorodimethylsilane [ka] To a solution of 5-(tert-butyl)-7-(ferrocen-1-yl)-6-methoxy-2-methyl-1H-indene (2.50 g, 6.24 mmol) in 70 ml of THF, nBuLi (2.5 M in hexane, 2.50 ml, 6.24 mmol) was added at −78° C. The resulting mixture was warmed to ambient temperature and stirred at this temperature for 1 h, then cooled to −78° C., and dichlorodimethylsilane (4.03 g, 31.2 mmol) was added in one portion. The resulting solution was stirred at room temperature overnight and then evaporated to dryness. The residue was dissolved in 50 ml of hot toluene, and the suspension thus obtained was filtered through a short pad of Celite. The filtrate was evaporated to dryness to give 2.64 g (86%) of a dark brown viscous oil, which was used further without additional purification. 1 H NMR (400 MHz, CDCl3): δ 7.62 (s, 1H), 7.46 (s, 1H), 4.94 (br. s., 1H), 4.87 (br. s., 1H), 4.60 - 4.45 (m, 2H), 4.30 (s, 5H), 3.64 (s, 1H), 3.40 (s, 3H), 2.49 (s., 3H), 1.60 (s, 9H), 0.62 (s, 3H), 0.37 (s, 3H). 13 C NMR (101MHz, CDCl3): δ 157.1, 144.3, 143.0, 137.4, 136.9, 128.3, 123.0, 120.2, 83.7, 70.8, 70.6, 69.5, 67.7, 67.6, 60.3, 49.1, 34.9, 31.1, 17.8, 1.3, -0.5.

[0142] N-tert-butyl-1-(6 / 5-tert-butyl-4 / 7-ferrocenyl-5 / 6-methoxy-2-methyl-1H-inden-1 / 3-yl)-dimethylsilanamine (A / B) [ka] To a solution of tert-butylamine (0.35 g, 4.79 mmol) in 30 ml of diethyl ether, nBuLi (2.5 M in hexane, 1.92 ml, 4.79 mmol) was added slowly at −30° C., and the resulting mixture was stirred at this temperature for 2 hours. A solution of (6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)chlorodimethylsilane (2.36 g, 4.79 mmol) in 20 ml of diethyl ether was added dropwise at −30° C. The resulting mixture was stirred at ambient temperature for 12 hours and then evaporated to dryness. The residue was dissolved in 50 ml of hot toluene, and the resulting suspension was filtered through a short pad of Celite. The filtrate was evaporated to dryness to give 2.60 g (99%) of the title material (an approximately 2.3:1 mixture of isomers A and B) as a dark red viscous oil, which was used further without additional purification. HRMS (ESI): [M+H] + C 31 H 44 FeNOSi + Calculated value: 530.2536; Measured value: 530.2531. 1 H NMR (400 MHz, CDCl3): δ 7.58 (s, 1H in B), 7.47 (s, 1H in A), 7.31 (s, 1H in A), 4.78 - 4.66 (m, 4H in A or B), 4.41 - 4.29 (m, 4H in A or B), 4.15 (s, 5H in A), 4.14 (s, 5H in B), 4.09 (s, 2H in B), 3.33 (s, 1H in A), 3.23 (s, 3H in B), 3.21 (s, 3H in A), 2.36 (s, 3H in B), 2.34 (s, 3H in A), 1.44 (s, 9H in A), 1.44 (s, 9H in B), 1.22 (s, 9H in A), 1.22 (s, 9H in B), 0.64 (br. s., 1H in A), 0.50 (s, 3H in B), 0.25 (s, 3H in B), 0.18 (s, 3H in A), 0.03 (s, 3H in A). 13C NMR (101MHz, CDCl3): δ 157.3, 156.5, 147.0, 144.6, 144.3, 143.2, 142.9, 140.0, 137.7, 137.2, 136.6, 128.4, 126.6, 123.1, 122.3, 120.4, 120.0, 84.0, 70.8, 70.7, 70.6, 69.3, 69.3, 69.2, 69.1, 67.5, 67.4, 67.3, 67.2, 60.5, 50.3, 49.6, 49.3, 35.1, 33.8, 31.4, 31.3, 18.4, 17.9, 1.4, 1.2, -0.3, -0.3.

[0143] (dimethylsilanediyl)(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 -tert-butylamido)dimethyltitanium (complex 11) [ka] To a solution of N-tert-butyl-1-(6 / 5-tert-butyl-4 / 7-ferrocenyl-5 / 6-methoxy-2-methyl-1H-inden-1 / 3-yl)dimethylsilanamine (2.43 g, 4.59 mmol) obtained above in 50 mL of diethyl ether, MeLi (1.6 M in diethyl ether, 14.3 mL, 22.9 mmol) was added dropwise at 0 °C. The resulting mixture was stirred at ambient temperature for 2 hours. Then, a solution of TiCl (0.50 mL, 0.87 g, 4.59 mmol) in 5 mL of hexane was added in one portion. The resulting mixture was stirred overnight at ambient temperature and then evaporated to dryness. To the residue, MeMgBr (2.9 M in diethyl ether, 4.75 mL, 13.8 mmol) and 100 mL of hexane were added. The mixture thus obtained was stirred overnight at ambient temperature, then filtered through a short pad of Celite and the filtrate was evaporated to dryness. The crude product was recrystallized from pentane at -30°C. Yield: 0.25 g (9%) of a dark brown solid. Elemental analysis: C 33 H 47Calculated values ​​for FeNOSiTi: C, 65.46; H, 7.82; N, 2.31. Found values: C, 65.69; H, 8.00; N, 2.13. 1 H NMR (400 MHz, CD2Cl2): δ7.82 (s, 1H), 7.34 (s, 1H), 4.95 (td, J = 1.3, 2.5 Hz, 1H), 4.65 (td, J = 1.2, 2.4 Hz, 1H), 4.47 (dt, J = 1.3, 2.4 Hz, 1H), 4.41 (dt, J = 1.2, 2.4 Hz, 1H), 4.22 - 4.16 (m, 5H), 3.22 (s, 3H), 2.22 (s, 3H), 1.51 (s, 9H), 1.35 (s, 9H), 0.68 (s, 3H), 0.61 (s, 3H), 0.60 (s, 3H), -0.55 (s, 3H). 13 C NMR (101 MHz, CD2Cl2): δ 159.3, 144.0, 141.7, 131.7, 131.3, 125.0, 123.1, 117.4, 89.3, 83.4, 71.1, 70.5, 70.0, 68.8, 68.3, 61.8, 36.0, 34.6, 32.2, 31.2, 23.2, 19.1, 14.5, 6.3, 6.0.

[0144] Example 12 (dimethylsilanediyl)(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(κ 1 Preparation of (tert-butylamido)dimethyltitanium (complex 12) Chloro(4-(ferrocen-1-yl)-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilane [ka] To a solution of 4-(ferrocen-1-yl)-2,2,6-trimethyl-1,2,3,5-tetrahydro-s-indacene (3.00 g, 7.85 mmol) in THF (70 ml), nBuLi (2.5 M in hexane, 3.14 ml, 7.85 mmol) was added at −78° C. The resulting mixture was warmed to ambient temperature, stirred for 1 h, and then cooled to −78° C. Further dichlorodimethylsilane (5.06 g, 39.2 mmol) was added in one portion. The resulting solution was stirred at room temperature overnight, the resulting mixture was evaporated, the residue was dissolved in hot toluene, and the resulting mixture was filtered through a short pad of Celite. The filtrate was evaporated. Yield: 3.10 g (84%) as a dark brown viscous oil, which was used further without additional purification. 1 H NMR (400 MHz, CDCl3): δ 7.49 (s, 1H), 7.21 (s, 1H), 4.68 - 4.57 (m, 2H), 4.37 (s, 2H), 4.17 (s, 5H), 3.57 (s, 1H), 3.04 - 2.69 (m, 4H), 2.37 (s, 3 H), 1.23 (s, 3 H), 1.12 (s, 3 H), 0.49 (s, 3 H), 0.24 (s, 3 H). 13 C NMR (101 MHz, CDCl3): δ 143.3, 141.6, 141.5, 139.4, 139.3, 128.4, 126.7, 118.4, 85.5, 70.1, 69.5, 69.3, 67.7, 67.4, 49.3, 48.7, 47.8, 40.1, 28.9, 28.8, 17.9, 1.3, -0.5.

[0145] N-tert-butyl-1-(4-ferrocenyl-2,6,6-trimethyl-1 / 3,5,6,7-tetrahydro-s-indacen-1-yl)-1,1-dimethylsilanamine (A / B) [ka] To a solution of tert-butylamine (0.46 g, 6.32 mmol) in 30 ml of diethyl ether, nBuLi (2.5 M in hexane, 2.52 ml, 6.32 mmol) was slowly added at −30° C., and the resulting mixture was stirred at this temperature for 2 hours. To the solution obtained above, chloro(4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)dimethylsilane (3.00 g, 6.32 mmol) in 20 ml of diethyl ether was added dropwise at −30° C. The resulting mixture was stirred at this temperature for 12 hours and then evaporated to dryness. The residue was dissolved in 30 ml of hot toluene, and the resulting suspension was filtered through a short pad of Celite. The filtrate was evaporated to dryness to give 2.54 g (91%) of the title product as a dark red, viscous oil. The product was found to be a mixture of two isomers, A and B, in a ratio of approximately 3.5:1 and was used further without additional purification. HRMS (ESI): [M+H] + C 31 H 42 FeNSi + Calculated value: 512.2430; Measured value: 512.2435. 1 H NMR (400 MHz, CDCl3): δ 7.48 (s, 1H in B), 7.43 (s, 1H in A), 7.22 (s, 1H in A), 4.80 - 4.73 (m, 1H in B), 4.73 - 4.62 (m, 3H in A or B), 4.42 - 4.35 (m, 4H in A or B), 4.21 (s, 5H in A), 4.19 (s, 5H in B), 3.64 - 2.74 (m, 13H in A and B), 3.42 (s, 1H in A), 2.40 (s, 3H in A), 1.34 - 1.20 (m, 27H in A), 1.17 (s, 3H in A), 0.68 (s, 1H in A), 0.53 (s, 6H in B), 0.27 (s, 3H in A), 0.07 (s, 3H in A). 13C NMR (101 MHz, CDCl3): δ 155.0, 145.7, 144.6, 144.4, 141.3, 138.8, 138.3, 138.0, 126.5, 125.9, 118.3, 117.1, 114.9, 86.1, 85.8, 70.0, 69.5, 69.2, 69.2, 69.1, 69.1, 69.1, 67.7, 67.5, 67.4, 67.2, 50.4, 49.6, 49.5, 49.0, 48.7, 48.0, 47.8, 47.7, 40.0, 40.0, 33.8, 33.6, 29.0, 28.9, 28.9, 28.8, 18.4, 17.6, 4.0, 1.3, -0.6, -3.5.

[0146] (dimethylsilanediyl)(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(κ 1 -tert-butylamido)dimethyltitanium (complex 12) [ka] To a solution of N-tert-butyl-1-(4-ferrocenyl-2,6,6-trimethyl-1 / 3,5,6,7-tetrahydro-s-indacen-1-yl)-1,1-dimethylsilanamine (2.94 g, 5.75 mmol) obtained above in 50 mL of diethyl ether, MeLi (1.6 M in diethyl ether, 18.0 mL, 28.7 mmol) was added dropwise at 0 °C. The resulting mixture was stirred at ambient temperature for 2 hours. Next, a solution of TiCl (0.63 mL, 1.09 g, 5.75 mmol) in 5 mL of hexane was added in one portion. The resulting mixture was stirred overnight and then evaporated to dryness. To the residue, MeMgBr (2.9 M in diethyl ether, 5.94 mL, 17.2 mmol) and 100 mL of hexane were added. The resulting mixture was stirred overnight at ambient temperature, then filtered through a short pad of Celite, and the filtrate was evaporated to dryness. The crude product was recrystallized from pentane at -30°C. Yield: 0.30 g (9%) of a dark brown solid. Elemental analysis: C33 H 45 Calculated values ​​for FeNSiTi: C, 67.46; H, 7.72; N, 2.38. Found values: C, 67.63; H, 7.90; N, 2.21. 1 H NMR (400 MHz, CD2Cl2): δ 7.65 (s, 1H), 7.18 (s, 1H), 4.81 - 4.75 (m, 1H), 4.72 - 4.67 (m, 1H), 4.46 - 4.41 (m, 1H), 4.41 - 4.38 (m, 1H), 4.17 (s, 5H), 3.07 - 2.91 (m, 2H), 2.87 - 2.53 (m, 2H), 2.17 (s, 3H), 1.53 (s, 9H), 1.28 (s, 3H), 0.99 (s, 3H), 0.68 (s, 3H), 0.62 (s, 3H), 0.59 (s, 3H), -0.43 (s, 3H). 13 C NMR (101MHz, CD2Cl2): δ 144.2, 140.8, 140.8, 135.8, 130.5, 130.4, 120.1, 117.5, 89.0, 85.4, 71.1, 69.8, 69.0, 68.7, 68.4, 49.5, 48.7, 47.8, 40.3, 34.6, 29.1, 28.7, 22.9, 19.1, 14.4, 6.5, 6.1.

[0147] Example 13 Synthesis of dimethylsilanediyl(4-ferrocenyl-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (complex 13) Synthesis of 8-ferrocenyl-6-methyl-1,2,3,5-tetrahydro-s-indacene (A) [ka] To a stirred mixture of 8-bromo-6-methyl-1,2,3,5-tetrahydro-s-indacene (0.511 g, 2.05 mmol), ferrocenylboronic acid (0.471 g, 2.05 mmol, 1 equiv.), potassium carbonate (0.624 g, 4.51 mmol, 2.2 equiv.), 1,3,5,7-tetramethyl-8-phenyl-2,4,6-trioxa-8-phosphatricyclo[3.3.1.13,7]decane (0.018 g, 62 μmol, 0.03 equiv.), and bis(dibenzylideneacetone)palladium (0.012 g, 21 μmol, 0.01 equiv.) in tetrahydrofuran (10 mL) was added nitrogen-sparged water (4 mL). The reaction vessel was sealed and the reaction was heated to 80 °C overnight. The reaction was concentrated in vacuo. The residue was partitioned between dichloromethane and water. The dichloromethane layer was collected and concentrated under vacuum. The residue was purified by silica gel column chromatography to give the product (164 mg, 22% yield). 1 H NMR (400 MHz, C6D6): δ 7.12 (s, 1H), 6.46 (s, 1H), 4.62 (s, 2H), 4.19 (s, 2H), 3.97 (s, 5H), 3.37 (s, 2H), 3.15 (t, 2H, J = 7.2 Hz), 2.86 (t, 2H, J = 7.4 Hz), 2.02-1.87 (m, 5H).

[0148] Dimethyl(4-ferrocenyl-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(2,3,4,5-tetramethylcyclopentadienyl)silane (B) [ka] To a pre-cooled, stirred solution of 8-ferrocenyl-6-methyl-1,2,3,5-tetrahydro-s-indacene (A) (0.164 g, 463 μmol) in diethyl ether (10 mL) was added n-butyllithium (0.29 mL, 1.64 M in hexanes, 1 equiv.). The reaction was stirred for 1 hour at room temperature. The reaction was filtered through a plastic fritted funnel. The filtered solid was collected and concentrated under high vacuum to give a solid (0.084 g, 23.3 μmol). The solid was suspended in diethyl ether (5 mL). To this stirred suspension was added a solution of [dimethyl-(2,3,4,5-tetramethylcyclopentadien-1-yl)silyl]trifluoromethanesulfonate (0.082 g, 250 μmol, 1.1 equiv.). The reaction was stirred for 1 hour at room temperature. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (50 mL) and filtered over Celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give the product as an orange foam (70 mg, 28% yield, two steps). 1 H NMR (400 MHz, C6D6): δ 7.63. (s, 1H), 7.36 (s, 1H), 4.68 (s, 1H), 4.63 (s, 1H), 4.22 (s, 2H), 4.14 (s, 5H), 3.66 (s, 1H), 3.30 (s, 1H), 3.12-2.81 (m, 4H), 2.19 (s, 3H), 2.00 (s, 3H), 1.93 (s, 3H), 1.91-1.82 (m, 8H), -0.15 (s, 3H), -0.18 (s, 3H).

[0149] Dimethylsilanediyl(4-ferrocenyl-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (Complex 13) [ka] To a pre-cooled, stirred solution of dimethyl(4-ferrocenyl-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)(2,3,4,5-tetramethylcyclopentadienyl)silane (B) (70 mg, 0.13 mmol) in diethyl ether (5 mL) was added n-butyllithium (0.16 mL, 1.64 M in hexanes, 0.26 mmol, 2.0 equiv.). The reaction was stirred for 45 minutes at room temperature. Zirconium chloride (31 mg, 0.13 mmol, 1.0 equiv.) and toluene (2 mL) were then added. The reaction was stirred for 17 hours at room temperature. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was extracted with dichloromethane (2 × 5 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was stirred in pentane (2 mL) until the mixture formed an orange suspension. The mixture was concentrated under a stream of nitrogen and then under high vacuum to give the product as a red-orange solid (82 mg, 90% yield). 1 H NMR (400 MHz, CD2Cl2): δ 7.50 (s, 1H), 7.31 (s, 1H), 4.76 (s, 1H), 4.71 (s, 1H), 4.41 (s, 1H), 4.36 (s, 1H), 4.14 (s, 5H), 3.21-2.99 (m, 2H), 2.95-2.82 (m, 1H), 2.80-2.68 (m, 1H), 2.31 (s, 3H), 2.17-1.99 (m, 5H), 1.96 (s, 3H), 1.92-1.74 (m, 8H), 1.19 (s, 3H), 1.09 (s, 3H).

[0150] Example 14 Synthesis of dimethylsilanediyl(4-ferrocenyl-2-methylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (complex 14) 4-Ferrocenyl-2-methylindene (C) [ka] To a stirred solution of ferrocene (1.78 g, 9.57 mmol) in tetrahydrofuran (50 mL) cooled to −78° C., tert-butyllithium (11.1 mL, 1.72 M in pentane, 19.1 mmol, 2.0 equiv.) was added dropwise over 10 minutes. The reaction was then warmed to −20° C. and stirred for 1 hour. The reaction was then cooled to −78° C. Zinc(II) chloride (1.43 g, 10.5 mmol, 1.10 equiv.) was then added. The reaction was then allowed to warm to room temperature. Bis(tri-tert-butylphosphine)palladium(0) (0.491 g, 0.957 mmol, 0.10 equiv.) and 4-bromo-2-methylindene (2.00 g, 9.57 mmol, 1 equiv.) were then added. The reaction was stirred and heated at reflux overnight. The reaction was cooled to room temperature, then poured onto ice water (100 mL) and extracted with dichloromethane (3 x 50 mL). The combined dichloromethane extracts were dried over anhydrous sodium sulfate and filtered through a pad of silica. The filtrate was concentrated under vacuum. The resulting crude product was purified by silica gel column chromatography (4% ethyl acetate in isohexane) to give the product as a red-orange solid (1.86 g, 62% yield, mixture of isomers). Major isomer 1 H NMR (400 MHz, C6D6): δ 7.36 (dd, 1H, J = 7.7, 1.1 Hz), 7.20 (t, 1H, J = 7.6 Hz), 7.13 (dd, 1H, J = 7.4, 1.1 Hz), 6.52-6.48 (m, 1H), 4.71 (t, 2H, J = 1.9 Hz), 4.32 (t, 2H, J = 1.9 Hz), 4.07 (s, 5H), 3.43 (s, 2H), 2.19 (s, 3H).

[0151] Synthesis of dimethyl(4-ferrocenyl-2-methylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)silane (D) [ka] To a pre-cooled, stirred solution of 4-ferrocenyl-2-methylindene (C) (0.985 g, 3.13 mmol) in diethyl ether (30 mL) was added n-butyllithium (2.0 mL, 1.64 M in hexanes, 3.3 mmol, 1 equiv.). The reaction was stirred for 1 hour at room temperature. The reaction was filtered through a plastic fritted funnel. The filtered solid was collected and concentrated under high vacuum. In a separate flask, to a stirred solution of [dimethyl-(2,3,4,5-tetramethylcyclopentadien-1-yl)silyl]trifluoromethanesulfonate (0.760 g, 2.31 mmol, 1 equiv.) in diethyl ether (10 mL) was added a suspension of the isolated solid in diethyl ether (20 mL, washed with an additional 10 mL). The reaction was stirred for 1 hour at room temperature. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2 x 5 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to give the product as an orange-red foam (0.963 g, 62% yield). 1 H NMR (400 MHz, C6D6): δ 7.53 (d, 1H, J = 7.8 Hz), 7.37 (d, 1H, J = 7.5 Hz), 7.29 (s, 1H), 7.12 (t, 1H, J = 7.6 Hz), 4.67 (s, 1H), 4.65 (s, 1H), 4.19 (s, 2H), 4.05 (s, 5H), 3.61 (s, 1H), 3.20 (s, 1H), 2.12 (s, 3H), 1.95 (s, 3H), 1.89 (s, 3H), 1.83 (s, 6H), -0.21 (s, 3H), -0.22 (s, 3H).

[0152] Dimethylsilanediyl(4-ferrocenyl-2-methylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (Complex 14) [ka] To a pre-cooled, stirred solution of dimethyl(4-ferrocenyl-2-methylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)silane (D) (0.963 g, 1.96 mmol) in diethyl ether (50 mL) was added n-butyllithium (2.4 mL, 1.64 M in hexanes, 3.9 mmol, 2 equiv.). The reaction was stirred for 45 minutes at room temperature. Zirconium chloride (0.456 g, 1.96 mmol, 1 equiv.) was then added, and residual zirconium chloride was washed into the reaction with toluene (3 mL). The reaction was stirred for an additional 16 hours at room temperature. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was extracted with dichloromethane (2 × 20 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was stirred in pentane (20 mL). The resulting suspension was concentrated under a stream of nitrogen and then under high vacuum to give the product as a red-orange solid (1.199 g, 94% yield). 1 H NMR (400 MHz, CD2Cl2): δ 7.49 (d, 1H, J = 8.6 Hz), 7.38 (d, 1H, J = 7.0 Hz), 7.33 (s, 1H), 6.91 (ddd, 1H, J = 8.7, 7.1, 1.7 Hz), 4.73 (s, 1H), 4.69 (s, 1H), 4.36 (s, 2H), 4.13 (s, 4H), 4.11-3.88 (br s, 1H), 2.32 (s, 3H), 2.07 (s, 3H), 1.96 (s, 3H), 1.86 (s, 3H), 1.85 (s, 3H), 1.19 (s, 3H), 1.10 (s, 3H).

[0153] Example 15 Synthesis of dimethylsilanedi(4-ferrocenyl-2-isopropylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (complex 15) 4-Ferrocenyl-2-isopropylindene (E) [ka] To a stirred solution of ferrocene (1.57 g, 8.43 mmol) and potassium tert-butoxide (0.115 g, 1.02 mmol, 0.122 equiv.) in tetrahydrofuran (30 mL) cooled to −78° C., tert-butyllithium (11.2 mL, 1.5 M in pentane, 16.8 mmol, 1.99 equiv.) was added dropwise over 10 minutes. The reaction was then warmed to −20° C. and stirred for 1 hour. The reaction was then recooled to −78° C., and zinc(II) chloride (1.26 g, 9.24 mmol, 1.1 equiv.) was added. The reaction was allowed to warm to room temperature. Bis(tri-tert-butylphosphine)palladium(0) (0.433 g, 843 μmol, 0.1 equiv.) and 4-bromo-2-isopropylindene (2.00 g, 8.43 mmol, 1 equiv.) were then added along with additional tetrahydrofuran (10 mL). The reaction was stirred and heated to reflux for 14 hours. The reaction was cooled to room temperature. The reaction was poured onto water (100 mL). The mixture was partially concentrated under vacuum to remove tetrahydrofuran. The resulting mixture was poured into a separatory funnel, and the remaining contents of the flask were rinsed into the separatory funnel with pentane (100 mL). The contents of the separatory funnel were shaken, and the organic layer was collected. The aqueous layer was further extracted with pentane (2×100 mL). The combined pentane extracts were dried over anhydrous sodium sulfate. The mixture was filtered through a pad of silica and further extracted with additional pentane (approximately 50 mL). The combined pentane filtrate was concentrated in vacuo to give a red oil, which was purified by silica gel column chromatography (4% ethyl acetate in isohexane) to give the product as a viscous red oil (1.800 g, 62% yield, mixture of isomers). Major isomer 1H NMR (400 MHz, C6D6): δ 7.48 (d, 1H, J = 7.6 Hz), 7.29 (t, 1H, J = 7.6 Hz), 7.22 (d, 1H, J = 7.4 Hz), 6.46 (s, 1H), 4.61 (s, 2H), 4.1 (s, 2H), 4.01 (s, 1H), 3.95 (s, 4H), 3.37 (s, 2H), 2.56 (septet, 1H, J = 6.8 Hz), 1.10 (d, 6H, J = 6.9 Hz).

[0154] Lithium 4-ferrocenyl-2-isopropylindenide (F) [ka] To a pre-cooled, stirred solution of 4-ferrocenyl-2-isopropylindene (E) (1.800 g, 5.26 mmol) in diethyl ether (50 mL) was added n-butyllithium (3.2 mL, 1.64 M in hexanes, 5.3 mmol, 1 equiv.). The reaction was stirred for 45 minutes at room temperature. The reaction was filtered over a plastic fritted funnel. The filtered solid was collected and concentrated under high vacuum to give the product as an orange solid (1.494 g, 82% yield). 1 H NMR (400 MHz, C4D8O): δ 7.16 (d, 1H, J = 7.9 Hz), 6.76 (d, 1H, J = 6.9 Hz), 6.42 (t, 1H, J = 7.4 Hz), 6.30 (s, 1H), 5.86 (s, 1H), 4.80 (s, 2H), 4.16 (s, 2H), 4.02 (s, 5H), 3.09 (septet, 1H, J = 7.0 Hz), 1.34 (d, 6H, J = 7.2 Hz).

[0155] Dimethyl(4-ferrocenyl-2-isopropylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)silane (G) [ka] To a pre-cooled, stirred suspension of lithium 4-ferrocenyl-2-isopropylindenide (F) (0.917 g, 2.63 mmol, 1.02 equiv.) in diethyl ether (50 mL) was added [dimethyl-(2,3,4,5-tetramethylcyclopentadien-1-yl)silyl]trifluoromethanesulfonate (0.844 g, 2.57 mmol) along with additional diethyl ether (5 mL). The reaction was stirred for 1.5 hours at room temperature. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (50 mL, then 20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to give the product as an orange foam (1.301 g, 97% yield). 1 H NMR (400 MHz, C6D6): δ 7.52 (d, 1H, J = 7.6 Hz), 7.45 (s, 1H), 7.39 (d, 1H, J = 7.5 Hz), 7.12 (t, 1H, J = 7.6 Hz), 4.70 (s, 2H), 1.49 (s, 2H), 4.07 (s, 5H), 3.87 (s, 1H), 3.21 (s, 1H), 2.79 (septet, 1H, J = 6.8 Hz), 2.01 (s, 3H), 1.89 (s, 3H), 1.84 (s, 3H), 1.82 (s, 3H), 1.35 (d, 3H, J = 6.6 Hz), 1.11 (d, 3H, J = 6.9 Hz).

[0156] Dimethylsilanediyl(4-ferrocenyl-2-isopropylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (Complex 15) [ka] To a pre-cooled, stirred solution of dimethyl(4-ferrocenyl-4-isopropylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)silane (G) (1.301 g, 2.50 mmol) in diethyl ether (50 mL) was added n-butyllithium (3.0 mL, 1.64 M in hexanes, 4.9 mmol, 2 equiv.). The reaction was stirred for 30 minutes at room temperature. Zirconium chloride (0.582 g, 2.50 mmol, 1 equiv.) was then added along with toluene (5 mL). The reaction was stirred for 2.5 days at room temperature. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was extracted with dichloromethane and filtered over Celite. The filtrate was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was stirred in pentane (20 mL). The resulting suspension was concentrated under a stream of nitrogen and then under high vacuum to give the product (1.617 g, 95% yield). 1 H NMR (400 MHz, CD2Cl2): δ 7.55 (s, 1H), 7.51 (d, 1H, J = 8.6 Hz), 7.36 (d, 1H, J = 7.0 Hz), 6.91 (t, 1H, J = 7.9 Hz), 4.82 (s, 1H), 4.70 (s, 1H), 4.38 (s, 2H), 4.15 (s, 4H), 4.12-4.03 (m, 1H), 3.13 (septet, 1H, J = 6.9 Hz), 2.02 (s, 3H), 1.97 (s, 3H), 1.87 (s, 6H), 1.44 (d, 3H, J = 6.6 Hz), 1.21 (s, 3H), 1.18 (d, 3H, J = 6.3 Hz), 1.13 (s, 3H).

[0157] Preparation of the complex 1-BF4 0.125 g of complex 1 was placed in a small vial equipped with a stir bar and dissolved in methylene chloride (approximately 5 mL). With stirring, 0.038 g of nitrosonium tetrafluoroborate (2 equivalents) was added, and the mixture was stirred for 1 hour. After 1 hour, the resulting dark red mixture was filtered over Celite. The solvent was removed to give a dark red / brown powder, which was further washed with pentane (2 x 5 mL) and dried under vacuum. This catalyst was used in polymerization without further purification.

[0158] Preparation of the complex 14-BF4 0.150 g of complex 14 was placed in a small vial equipped with a stir bar and dissolved in methylene chloride (approximately 5 mL). With stirring, 0.027 g of nitrosonium tetrafluoroborate (1 equivalent) was added, and the mixture was stirred for 1 hour. After 1 hour, the resulting dark red mixture was filtered over Celite. The solvent was removed to give a dark red / brown powder, which was further washed with pentane (2 × 5 mL) and dried under vacuum. This catalyst was used in polymerization without further purification.

[0159] Preparation of silica-supported MAO (SMAO) In a celstirrer, 10.0 g of 200°C calcined silica (DM-L403, Asahi Glass) was suspended in approximately 100 mL of anhydrous toluene and cooled to -20°C in a freezer. After approximately 30 minutes of cooling, a 30 wt% solution of MAO (15.8 g in toluene) was slowly added (over 10 minutes) to the stirred silica mixture. The mixture was allowed to warm to room temperature (exothermally) with stirring for 1.5 hours. After 1.5 hours, the temperature was increased to 100°C, and the reaction was stirred for an additional 2.5 hours. The temperature was then reduced to 55°C, and the mixture was then filtered on a glass frit. The SMAO was then washed with 2 x 50 mL of toluene and 2 x 50 mL of pentane and dried under vacuum for 1 hour. Yield: 14.1 g

[0160] Preparation of supported catalysts for laboratory reactor polymerization. Supported Complex 1: 0.55 g of DM-L403 SMAO was suspended in toluene (6 mL) and placed on a shaker. TIBAL (0.28 mL of a 1 M solution) was then added, and the mixture was shaken for 15 minutes. Complex 1 (10.2 mg in approximately 2 mL of toluene) was then added dropwise. The slurry was shaken for 2.5 hours. After 2.5 hours, the solid was filtered, washed with toluene (2 × 5 mL) and pentane (2 × 5 mL), and dried under vacuum to yield the supported catalyst. 0.2 g of the solid catalyst was slurried in mineral oil to make a 5 wt. % slurry prior to reactor polymerization testing. Supported Complex 13: 0.55 g of DM-L403 SMAO was suspended in toluene (6 mL) and placed on a shaker. TIBAL (0.28 mL of a 1 M solution) was then added, and the mixture was shaken for 15 minutes. Complex 13 (8.3 mg in approximately 2 mL of toluene) was then added dropwise. The slurry was shaken for 2.5 hours. After 2.5 hours, the solid was filtered, washed with toluene (2 × 5 mL) and pentane (2 × 5 mL), and dried under vacuum to yield the supported catalyst. 0.2 g of the solid catalyst was slurried in mineral oil to make a 5 wt. % slurry prior to reactor polymerization testing. Supported Complex 14: 0.55 g of DM-L403 SMAO was suspended in toluene (6 mL) and placed on a shaker. TIBAL (0.28 mL of a 1 M solution) was then added, and the mixture was shaken for 15 minutes. Complex 14 (7.9 mg in approximately 2 mL of toluene) was then added dropwise. The slurry was shaken for 2.5 hours. After 2.5 hours, the solid was filtered, washed with toluene (2 × 5 mL) and pentane (2 × 5 mL), and dried under vacuum to yield the supported catalyst. 0.2 g of the solid catalyst was slurried in mineral oil to make a 5 wt. % slurry prior to reactor polymerization testing. Supported Complex 15: 0.55 g of DM-L403 SMAO was suspended in toluene (6 mL) and placed on a shaker. TIBAL (0.28 mL of a 1 M solution) was then added, and the mixture was shaken for 15 minutes. Complex 15 (8.2 mg in approximately 2 mL of toluene) was then added dropwise. The slurry was shaken for 2.5 hours. After 2.5 hours, the solid was filtered, washed with toluene (2 × 5 mL) and pentane (2 × 5 mL), and dried under vacuum to yield the supported catalyst. 0.2 g of the solid catalyst was slurried in mineral oil to make a 5 wt. % slurry prior to reactor polymerization testing.

[0161] Small-scale polymerization example Toluene (ExxonMobil Chemical - anhydrous, stored under N2) (98%) was used to make a solution of the catalyst precursor, which was typically 0.5 mmol / L. The solvent, polymerization-grade toluene and / or isohexane, was provided by ExxonMobil Chemical Co. and purified by passage through a series of two 500-cc Oxyclear cylinders manufactured by Labclear (Oakland, Calif.), followed by two 500-cc columns packed with dry 3 Å molecular sieves (8–12 mesh; Aldrich Chemical Company) and two 500-cc columns packed with dry 5 Å molecular sieves (8–12 mesh; Aldrich Chemical Company).

[0162] 1-Octene (C8; 98%, Aldrich Chemical Company) was dried by stirring overnight over NaK, followed by filtration through basic alumina (Aldrich Chemical Company, Brockman Basic 1).

[0163] Polymerization-grade ethylene (C2) was used and further purified by passage through a series of columns: a 500-cc Oxyclear cylinder from Labclear (Oakland, Calif.), followed by a 500-cc column packed with dry 3 Å molecular sieves (8–12 mesh; Aldrich Chemical Company), and a 500-cc column packed with dry 5 Å molecular sieves (8–12 mesh; Aldrich Chemical Company). Polymerization-grade propylene (C3) was used and further purified by passage through a series of columns: a 2250-cc Oxiclear cylinder from Labclear, followed by a 2250-cc column packed with 3 Å molecular sieves (8–12 mesh; Aldrich Chemical Company), then two 500-cc columns in series packed with 5 Å molecular sieves (8–12 mesh; Aldrich Chemical Company), then a 500-cc column packed with Selexsorb CD (BASF), and finally a 500-cc column packed with Selexsorb COS (BASF).

[0164] Activation of the catalyst precursor was with either methylalumoxane (MAO, 10 wt% in toluene, Albemarle Corp.; activator ID=A1) or dimethylanilinium tetrakisperfluorophenylborate (Boulder Scientific or Albemarle Corp.; activator ID=A2). MAO was used as a 0.5 wt% or 1.0 wt% solution in toluene. The micromoles of MAO reported in the experimental section are based on the micromoles of aluminum in MAO. The formula weight of MAO is 58.0 g / mole. Dimethylanilinium tetrakisperfluorophenylborate was typically used as a 0.5 mmol / L solution in toluene.

[0165] For polymerization experiments using dimethylanilinium tetrakisperfluorophenylborate, tri-n-octylaluminum (TnOAl, untreated, AkzoNobel) was also used as a scavenger before introducing the activator and catalyst precursor into the reactor. TnOAl was typically used as a 5 mmol / L solution in toluene.

[0166] Description and preparation of small-scale reactor Polymerizations were carried out in an inert atmosphere (N2) drybox using an autoclave equipped with an external heater for temperature control, a glass insert (internal reactor volume = 23.5 mL for C2 and C2 / C8 experiments; 22.5 mL for C3 and C2 / C3 experiments), a septum inlet, regulated supplies of nitrogen, ethylene, and propylene, and a single-use PEEK mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110 or 115 °C for 5 h, then at 25 °C for 5 h.

[0167] Small-scale ethylene polymerization (PE) or ethylene / 1-octene copolymerization (EO) : The reactor was prepared as described above and then purged with ethylene. For MAO (activator ID = A1) activation experiments, toluene or isohexane, 1-octene (100 μL, if used), and the activator (MAO) were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to the process temperature (80°C) with stirring at 800 RPM, and ethylene was charged to the process pressure (75 psig = 618.5 kPa or 200 psig = 1480.3 kPa). The catalyst precursor solution was then added to the reactor via syringe under process conditions. For dimethylanilinium tetrakisperfluorophenylborate (activator ID = A2) activation experiments, toluene or isohexane, 1-octene (100 μL, if used), and the scavenger (TnOAl, 0.5 μmol) were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (80°C) with stirring at 800 RPM, and ethylene was charged to process pressure (75 psig = 618.5 kPa or 200 psig = 1480.3 kPa). The activator solution, followed by the catalyst precursor solution, was injected into the reactor via syringe under process conditions. During the polymerization, ethylene was admitted to the autoclave (using a computer-controlled solenoid valve) to maintain the reactor gauge pressure (+ / - 2 psig). The reactor temperature was monitored and typically maintained within + / - 1°C. The polymerization was terminated by adding a compressed dry air gas mixture of approximately 50 psi to the autoclave for approximately 30 seconds. The polymerization was quenched after a predetermined cumulative amount of ethylene (maximum quench value in psid) had been added, or for a maximum polymerization time of 30 minutes. The reactor was then cooled and vented. The solvent was removed under vacuum, and the polymer was isolated. The reported yield includes the total mass of polymer and residual catalyst. Catalytic activities are reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g / mmol·hr). Ethylene homopolymerization experiments are summarized in Table 1, and ethylene / 1-octene copolymerization experiments are summarized in Table 2.

[0168] Small-scale propylene polymerization (PP) : The reactor was prepared as described above, then heated to 40°C and purged with propylene gas at atmospheric pressure. For MAO activation experiments, toluene or isohexane, MAO, and liquid propylene (1.0 mL) were added via syringe. The reactor was then heated to the process temperature (70°C or 100°C) while stirring at 800 RPM. The catalyst precursor solution was added to the reactor via syringe under process conditions. For dimethylanilinium tetrakisperfluorophenylborate or dimethylanilinium tetrakisperfluoronaphthylborate activation experiments, toluene or isohexane, liquid propylene (1.0 mL), and scavenger (TnOAl, 0.5 μmol) were added via syringe. The reactor was then brought to the process temperature (70°C or 100°C) while stirring at 800 RPM. The activator solution, followed by the catalyst precursor solution, was injected into the reactor via syringe under process conditions. The reactor temperature was monitored and typically maintained within ±1°C. Polymerization was terminated by adding a compressed dry air gas mixture of approximately 50 psi to the autoclave for approximately 30 seconds. Polymerization was quenched based on a predetermined pressure drop (maximum quench value) or for a maximum of 30 minutes. The reactor was cooled and vented. The solvent was removed under vacuum, and the polymer was isolated. The actual quench time (seconds) is reported as Quench Time (seconds). The reported yield includes the total mass of polymer and residual catalyst. Catalyst activity is reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g / mmol·hr). Propylene homopolymerization examples are reported in Table 3, and additional characterization is reported in Table 4.

[0169] Experimental reactor scale polymerization procedure (propylene bulk slurry) A 1 L autoclave reactor equipped with a mechanical stirrer was used for polymer preparation. Prior to the experiment, the reactor was placed under a nitrogen purge while a temperature of 90 °C was maintained for 30 min. After cooling back to ambient temperature, propylene feed (500 mL), scavenger (0.2 mL of 1 M TIBAL, triisobutylaluminum), and optional hydrogen (charged from a 50 mL bomb at the desired pressure) were introduced into the reactor and mixed for 5 min. The supported catalyst (typically 12.5–25.0 mg) was then introduced into the reactor by flushing a predetermined amount of catalyst slurry (5 wt. % in mineral oil) from the catalyst tube with 100 mL of liquid propylene. The reactor was maintained at room temperature for 5 min (prepolymerization stage), after which the temperature was increased to 70 °C. The reaction was allowed to proceed at that temperature for a period of time (typically 30 min). After the given time, the temperature was reduced to 25 °C, the excess propylene was vented, and the polymer granules were collected and dried overnight.

[0170] Small-scale polymer characterization For analytical testing, polymer sample solutions were prepared by dissolving the polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity, Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%, Aldrich) at 165 °C in a shaker oven for approximately 3 h. Typical concentrations of polymer in solution were 0.1-0.9 mg / mL, and BHT concentrations were 1.25 mg BHT / mL of TCB. Samples were cooled to 135 °C for testing.

[0171] High temperature size exclusion chromatography was performed using an automated "fast GPC" system as described in U.S. Pat. Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388, each of which is incorporated herein by reference. Molecular weights (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distributions (MWD = Mw / Mn), sometimes referred to as polymer polydispersity (PDI), were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD) and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 5,000 and 3,390,000). Alternatively, samples were measured by gel permeation chromatography using a Symyx Technology GPC equipped with a dual wavelength infrared detector and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 580 and 3,039,000). Three Polymer Laboratories PLgel 10 μm Mixed-B 300 × 7.5 mm columns in series were used to run samples (250 μL of polymer solution in TCB was injected into the system) at an eluent flow rate of 2.0 mL / min (135°C sample temperature, 165°C oven / column). No column expansion correction was used. Numerical analysis was performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. Obtained molecular weights were compared to linear polystyrene standards. Molecular weight data are reported in Tables 1, 2, 3, and 5 under the headings Mn, Mw, and PDI as defined above.

[0172] Differential scanning calorimetry (DSC) was performed on a TA-Q100 instrument to determine the melting points of the polymers. The samples were pre-annealed at 220°C for 15 minutes and then cooled to room temperature overnight. The samples were then heated to 220°C at a rate of 100°C / min and then cooled at a rate of 50°C / min. Melting points were taken during the heating period. The results are reported in Tables 1, 2, and 3 under the heading Tm (°C). Samples for infrared analysis were prepared by depositing the stabilized polymer solution onto a silanized wafer (part number S10860, Symyx). This method results in approximately 0.12–0.24 mg of polymer being deposited onto the wafer cell. Samples were then analyzed on a Brucker Equinox 55 FTIR spectrometer equipped with a Pike MappIR specular reflectance sample accessory. 5000 cm -1 ~500cm -1 The spectrum covering the spectral range of -1 32 scans were collected at a resolution of 100 s.

[0173] For ethylene-1-octene copolymer, it is about 1375 cm -1 The mass percent octene in the copolymer was determined via measurement of the methyl deformation band at 4321 cm. The peak height of this band was determined at approximately 4321 cm. -1 The peak heights were normalized by the bond and overtone bands at , which corrects for path length differences. The normalized peak heights were calculated as 1 Individual calibration curves from H NMR data were correlated to predict the mass % octene content within a concentration range of approximately 2-35 mass % octene. Typically, an R of 0.98 or greater was obtained. 2 A correlation is achieved. These figures are reported in Table 2 under the heading C8 wt %. 13 C NMR spectroscopy was used to characterize several polypropylene polymer samples produced in the experiments summarized in Tables 3 and 5. The data is summarized in Tables 4 and 6. Unless otherwise specified, 13 For C NMR spectroscopy, polymer samples were dissolved in d2-1,1,2,2-tetrachloroethane and analyzed by a 150 MHz13 Samples were recorded at 125°C using an NMR spectrometer at C NMR frequencies. Polymer resonance peaks are referenced at mmmm = 21.8 ppm. Calculations involved in characterizing polymers by NMR follow the work of F.A. Bovey, "Polymer Conformation and Configuration," Academic Press, New York, 1969, and J. Randall, "Polymer Sequence Determination, Carbon-13 NMR Method," Academic Press, New York, 1977.

[0174] Stereo defects, measured as "stereo defects / 10,000 monomer units," are calculated by multiplying the sum of the intensities of the mmrr, mmrm+rrmr, and rmrm resonance peaks by 5,000. The intensities used in the calculation are normalized to the total number of monomers in the sample. Methods for measuring 2,1 regio defects / 10,000 monomers and 1,3 regio defects / 10,000 monomers follow standard methods. Additional references include Grassi, A. et.al. Macromolecules, 1988, v. 21, pp. 617-622 and Busico et.al. Macromolecules, 1994, v. 27, pp. 7538-7543. Average mesomorphic length = 10000 / [(steric defects / 10000C) + (2,1-position defects / 10000C) + (1,3-position defects / 10000C)].

[0175] 1 1 H NMR data was obtained at either room temperature or 120°C (120°C shall be used for claims purposes) using 250 MHz, 400 MHz, or 500 MHz 1H frequency, collected in a 5 mm probe using a Varian spectrometer (for claims purposes, a proton frequency of 500 MHz is used, with polymer samples dissolved in 1,1,2,2-tetrachloroethane-d2 (TCE-d2) and transferred to 5 mm glass NMR tubes). Data were recorded using a maximum pulse width of 45°C, 5 seconds between pulses, and a signal average of 120 transients. The chemical shift region for olefins is defined as being between the following spectral regions: Values ​​reported in Table 6 are % vinylene, % trisubstituted (% trisub), % vinyl, and % vinylidene, with percentages being based on total olefinic unsaturation per 1000 carbon atoms. [Table 2]

[0176] The polymerization results are summarized in Tables 1, 2, 3, and 4 below. "Example No." refers to the example number. The following abbreviations are defined in the Example No. column heading: PE = polyethylene, EO = ethylene-1-octene copolymer, PP = polypropylene, CPE = comparative polyethylene, CEO = comparative ethylene-1-octene copolymer, and CPP = comparative polypropylene. Examples beginning with "C," such as CPP and CPE, are comparative examples. "Catalyst ID" identifies the catalyst precursor used in the experiment. The corresponding numbers identifying the catalyst precursor (also called catalyst precursor, complex, or compound) are found in the synthetic experiments section or below for comparative catalyst precursors. "Catalyst (μmol)" is the amount of catalyst precursor added to the reactor. In all experiments using dimethylanilinium tetrakisperfluorophenylborate (Activator ID=A2), the activator / catalyst precursor molar ratio was 1.1. In all experiments using MAO (Activator ID=A1) as the activator, a 500 Al / M molar ratio was used unless otherwise specified. T (°C) is the polymerization temperature, which was typically maintained within + / - 1°C. "Yield" is the polymer yield, not corrected for catalyst residues. "Quench time (sec)" is the actual duration of the polymerization run in seconds. The "quench value (psid)" for ethylene-based polymerization runs is the set maximum amount of ethylene uptake (conversion) for the run. If the polymerization quench time is shorter than the set maximum time, the polymerization is run until the set maximum ethylene uptake is reached. For propylene homopolymerization runs, the quench value indicates the maximum set pressure drop (conversion) of propylene (for PP runs) during the polymerization. Activity is reported in grams of polymer per mmol of catalyst per hour.

[0177] The comparative catalysts are as follows: C-1 is rac-dimethylsilylene-bis(2-methylindenyl)zirconium dichloride. C-2 is rac-dimethylsilylene-bis(2-methylindenyl)zirconium dimethyl. C-3 is rac-dimethylsilylene-bis(2-methylindenyl)hafnium dimethyl. C-4 is dimethylsilylene(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tert-butylamido)titanium dimethyl.

[0178] [Table 3-1] [Table 3-2] [Table 3-3] [Table 4-1] [Table 4-2] [Table 4-3] [Table 4-4] [Table 4-5] [Table 4-6] [Table 5-1] [Table 5-2] [Table 5-3] [Table 5-4] [Table 5-5] [Table 5-6] [Table 5-7] [Table 5-8] [Table 5-9] [Table 6-1] [Table 6-2] [Table 6-3] Table 5 shows laboratory reactor-scale slurry polymerization data using supported catalysts 1, 13, 14, and 15. Supported catalysts 1, 13, and 14 exhibited excellent particle morphology and activity when run in bulk propylene at 70°C. The polymers produced were isotactic and had a pentavalent element range of 0.687 to 0.926 (Table 6). Both supported catalyst compounds 13 and 15 exhibited higher than normal vinyl terminated chain end content (40% to 67%).

[0179] [Table 7]

[0180] [Table 8]

[0181] Small-scale, high-throughput polymerizations of propylene and ethylene-propylene were performed in solution using MAO activation. In addition to the data in Table 3, data from the high-throughput polymerizations are shown in Table 7. Both the oxidized species 1-BF4 and 14-BF4 demonstrate improvements in molecular weight capability for isotactic polypropylene (iPP) and ethylene-propylene (EP) rubbers. Furthermore, these molecules also promote higher crystallinity (Tm) compared to the parent complexes 1 and 14. For example, the versatility of these systems allowed all catalysts to exhibit excellent activity, producing polymers with a range of Mw (approximately 20-300 kDa), Tm (approximately 100-150 °C), and wt% ethylene in EP (approximately 20-50 wt%).

[0182] [Table 9-1] [Table 9-2]

[0183] Overall, metallocene catalyst compounds of the present disclosure having a ferrocene moiety at the 4-position of the aryl ligand have been found to provide polymers with high activity. The polymers formed may have one or more of high molecular weight, high comonomer incorporation, high melting temperature, narrow polydispersity index, and / or (in the case of polypropylene) isotacticity. Ethylene copolymers formed using the catalysts of the present disclosure may have high molecular weight and high comonomer incorporation, and high comonomer incorporation can improve the processability of the formed ethylene copolymer while maintaining most, if not all, of the mechanical property advantages provided by high molecular weight. Interestingly, isotactic polypropylene can be obtained. Furthermore, high activity of the catalysts of the present disclosure can be obtained even when the ferrocenyl substituent is located on the 6-membered indenyl ring, compared to the 5-membered indenyl ring, which is closer to the catalyst metal atom. The oxidation state of the iron atom of the catalyst compounds of the present disclosure can also be easily adjusted with an oxidizing or reducing agent, providing tunability and controllability of the polymer properties of polymers formed using the catalyst compounds of the present disclosure.

[0184] Unless otherwise specified, the phrases "consists essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether specifically mentioned herein or not, unless such other steps, elements, or materials affect the basic and novel characteristics of the disclosure, nor do they exclude impurities and variations normally associated with the elements and materials used.

[0185] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower limit may be combined with any upper limit to recite a range not explicitly recited, and similarly, a range from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, and similarly, a range from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Furthermore, a range includes all points or individual values ​​between its endpoints, even if not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit in combination with any other point or individual value, or any other lower or upper limit, to recite a range not explicitly recited.

[0186] All documents cited herein, including any priority documents and / or testing procedures, are incorporated herein by reference, unless inconsistent herewith. While forms of the disclosure have been illustrated and described, as is apparent from the general description and specific embodiments above, various modifications can be made without departing from the spirit and scope of the disclosure. Accordingly, no limitation of the disclosure is intended. Similarly, for purposes of U.S. law, the term "comprising" is considered synonymous with the term "including." Similarly, whenever the transitional phrase "comprising" precedes a composition, element, or group of elements, it is understood that the same composition or group of elements is also contemplated if the transitional phrase "consisting essentially of," "consisting of," "selected from the group consisting of," or "is" precedes the recitation of the composition, element, or group of elements, and vice versa. While the present disclosure has been described in terms of several embodiments and examples, those skilled in the art, having the benefit of this disclosure, will appreciate that other embodiments may be devised that do not depart from the scope and spirit of the present disclosure.

Claims

1. A catalyst compound represented by formula (I): 【Chemistry 1】 (In the formula, M is a metal atom of Groups 3 to 5 of the Periodic Table, a lanthanide metal atom, or an actinide metal atom; E is a substituted polycyclic arenyl ligand attached to M and substituted with at least one ferrocenyl substituent attached to the aromatic six-membered ring of the polycyclic arenyl ligand; A is a monoanionic ligand bound to M; n is 0 or 1; T is a bridging group that bonds to A and E and contains an element from Group 13, 14, 15, or 16 of the Periodic Table of the Elements, and is present when n is 1 and absent when n is zero; each occurrence of X is independently a monovalent anionic ligand, or two X's are joined together to form a metallocycle ring when attached to M, or two X's are joined together to form a chelating, diene, or alkylidene ligand; each occurrence of L is independently a Lewis base, or two L's joined together and attached to M form a bidentate Lewis base; X may be joined to L to form a monoanionic bidentate group; y is 1, 2, or 3; w is 0, 1, or 2; y+w is 4 or less.

2. 2. The catalyst compound of claim 1, wherein at least one ferrocenyl substituent is represented by formula (Ia): 【Chemistry 2】 (Wherein Fe is Fe(II) or Fe(III), R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 Each of R is independently hydrogen, hydrocarbyl, or any adjacent R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 may be joined to form one or more hydrocarbyl or heterocyclic rings each having 5, 6, 7, or 8 ring atoms; The dashed line indicates the bond of E in formula (I) to the polycyclic arenyl ligand; n' is the charge on Fe, where n' is zero if Fe is Fe(II) and +1 if Fe is Fe(III); Y, if present, is a non-coordinating anion having a charge of −1, and is present when q is 1 and n′ is +1, and is absent when q is 0 and n′ is 0.

3. 3. The catalyst compound of claim 2, wherein in formula (Ia) Fe is Fe(II), n' is 0, and q is 0.

4. 3. The catalyst compound of claim 2, wherein Fe in formula (Ia) is Fe(III), n' is +1, and q is 1.

5. 5. The catalyst compound of claim 4, wherein Y is selected from the group consisting of tetrakis(3,5-bis(trifluoromethyl)phenylborate), tetrafluoroborate, antimony hexafluoride, phosphorus hexafluoride, tetrakis(perfluorophenylborate), and tetraphenylborate.

6. R in formula (Ia) 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 The catalyst compound of any one of claims 2 to 5, wherein each of is hydrogen.

7. 7. The catalyst compound of any one of claims 2 to 6, wherein E is selected from the group consisting of substituted indenyl, fluorenyl, cyclopenta[b]naphthalenyl, cyclopenta[a]naphthalenyl, tetrahydro-s-indacenyl, and tetrahydro-as-indacenyl.

8. 8. The catalyst compound according to any one of claims 1 to 7, wherein at least one ferrocenyl substituent of formula (Ia) is located at the 4-position of E.

9. 9. The catalyst compound of any one of claims 1 to 8, wherein A is selected from the group consisting of substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, cyclopenta[b]naphthalenyl, cyclopenta[a]naphthalenyl, tetrahydro-s-indacenyl, and tetrahydro-as-indacenyl.

10. A is Shiki JR'' m-1-n wherein J is a heteroatom from Group 15 of the Periodic Table of the Elements having a coordination number of 3 or a heteroatom from Group 16 having a coordination number of 2, and each occurrence of R″ is independently hydrocarbyl; m is the coordination number of the heteroatom J such that “m-1-n” indicates the number of R″ substituents attached to J, and n is 0 or 1.

11. The catalyst compound according to any one of claims 1 to 6, represented by formula (IIa) or (IIb): 【Transformation 3】 (In the formula, M, T, L, X, y, and w in formulas (IIa) and (IIb) are as described for formula (I); R in formula (IIa) and (IIb) 4 , R 5 , R 6 and R 7 is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a heteroatom or heteroatom-containing group, or a ferrocenyl substituent, with the proviso that R 4 , R 5 , R 6 or R 7 is a ferrocenyl substituent, and an adjacent R 4 , R 5 , R 6 , and R 7 may be joined to form one or more substituted hydrocarbyl or heterocyclic rings each having 5, 6, 7, or 8 ring atoms; R in formula (IIa) and formula (IIb) 10 , R 11 , R 12 and R 13 Each of R is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a heteroatom or heteroatom-containing group, or a ferrocenyl substituent, and any adjacent R is not ferrocenyl. 10 , R 11 , R 12 and R 13 may be joined to form one or more substituted or unsubstituted hydrocarbyl or heterocyclic rings each having 5, 6, 7, or 8 ring atoms; R in formula (IIa) and formula (IIb) 2 , R 3 , R 8 , and R 9 Each of R is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a heteroatom, or a heteroatom-containing group, and any two adjacent R 2 , R 3 , R 8 , and R 9 may be joined to form one or more substituted or unsubstituted hydrocarbyl or heterocyclic rings each having 5, 6, 7, or 8 ring atoms; R in formula (IIb) 1 and R 14 Each of R is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a heteroatom, or a heteroatom-containing group, and any two adjacent R 1 , R 2 , R 8 , and R 14 may be joined to form one or more substituted or unsubstituted hydrocarbyl or heterocyclic rings, each having 5, 6, 7, or 8 ring atoms.

12. The catalyst compound according to any one of claims 1 to 6, represented by formula (IIIa) or (IIIb): 【Chemistry 4】 (In the formula, M, T, L, X, y, and w in formula (IIIa) and formula (IIIb) are as described for formula (I); R in formula (IIIa) and formula (IIIb) 4 , R 5 , R 6 and R 7 is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a heteroatom or heteroatom-containing group, or a ferrocenyl substituent, with the proviso that R 4 , R 5 , R 6 or R 7 is a ferrocenyl substituent, and an adjacent R 4 , R 5 , R 6 , and R 7 may be joined to form one or more substituted hydrocarbyl or heterocyclic rings each having 5, 6, 7, or 8 ring atoms; R 2 , R 3 , R 15 , R 16 , R 17 , and R 18 Each of R is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a heteroatom, or a heteroatom-containing group, and any two adjacent R 2 , R 3 , R 15 , R 16 , R 17 , and R 18 may be joined to form one or more substituted or unsubstituted hydrocarbyl or heterocyclic rings each having 5, 6, 7, or 8 ring atoms; R in formula (IIIb) 1 and R 19 Each of R is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a heteroatom, or a heteroatom-containing group, and any two adjacent R 1 , R 2 , R 15 , R 18 , and R 19 may be joined to form one or more substituted or unsubstituted hydrocarbyl or heterocyclic rings, each having 5, 6, 7, or 8 ring atoms.

13. The catalyst compound according to any one of claims 1 to 6, represented by formula (IVa) or (IVb): 【Transformation 5】 (M, T, L, X, y, and w in formulas (IVa) and (IVb) are as described for formula (I); R 4 , R 5 , R 6 and R 7 is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a heteroatom or heteroatom-containing group, or a ferrocenyl substituent, with the proviso that R 4 , R 5 , R 6 or R 7 is a ferrocenyl substituent, and an adjacent R 4 , R 5 , R 6 , and R 7 may be joined to form one or more substituted hydrocarbyl or heterocyclic rings each having 5, 6, 7, or 8 ring atoms; R in formula (IVa) and formula (IVb) 2 and R 3 Each of R is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a heteroatom, or a heteroatom-containing group, and any two adjacent R 2 , and R 3 may be joined to form one or more substituted or unsubstituted hydrocarbyl or heterocyclic rings each having 5, 6, 7, or 8 ring atoms; J is a heteroatom with a coordination number of 3 from Group 15 or a heteroatom with a coordination number of 2 from Group 16 of the Periodic Table of the Elements; R in formula (IVb) 1 are independently hydrogen, substituted or unsubstituted hydrocarbyl, a heteroatom, or a heteroatom-containing group, and any two adjacent R 1 and R 2 may be joined to form one or more substituted or unsubstituted hydrocarbyl or heterocyclic rings each having 5, 6, 7, or 8 ring atoms; each R" is independently substituted or unsubstituted hydrocarbyl, and m is the coordination number of the heteroatom J, where "m-2" and "m-1" indicate the number of R" substituents attached to J.

14. 14. The catalyst compound of claims 10 and 13, wherein J in formula (IIIa), formula (IIIb), formula (IVa), and formula (IVb) is nitrogen and each occurrence of R″ is selected from the group consisting of tert-butyl, neopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, adamantan-1-yl, adamantan-2-yl, norborn-1-yl, norborn-2-yl, benzyl, and ethylphenyl.

15. 15. The catalyst compound of any one of claims 1 to 14, wherein each occurrence of X in Formula (I), Formula (IIa), Formula (IIb), Formula (IIIa), Formula (IIIb), Formula (IVa), and Formula (IVb) is independently selected from the group consisting of methyl, benzyl, trimethylsilyl, methylene(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamide, diethylamide, dipropylamide, and diisopropylamide.

16. Each occurrence of L in formula (I), formula (IIa), formula (IIb), formula (IIIa), formula (IIIb), formula (IVa), and formula (IVb) is independently selected from the group consisting of Et 2 O,MeOtBu,Et 3 N, PhNMe 2 , MePh 2 16. The catalyst compound of any one of claims 1 to 15, selected from the group consisting of N, tetrahydrofuran, and methyl acetate.

17. The catalyst compound according to any one of claims 1 to 16, wherein M in formula (I), formula (IIa), formula (IIb), formula (IIIa), formula (IIIb), formula (IVa), and formula (IVb) is Zr, Hf, or Ti.

18. n is 1, and T in formula (I), formula (IIa), formula (IIIa), and formula (IVa) is CH 2 , C.H. 2 CH 2 , C(CH 3 ) 2 , C.P.h. 2 , SiMe 2 , SiPh 2 , SiMePh, Si(CH 2 ) 3 , Si(CH 2 ) 4 , and Si(CH 2 ) 5 The catalyst compound according to any one of claims 1 to 17, selected from the group consisting of:

19. The catalyst compound of formula (I) or formula (IIa) rac-dimethylsilanediyl-bis(η 5 (4-ferrocenyl-2-methylinden-1-yl)zirconium dichloride, rac-dimethylsilanediyl-bis(η 5 (4-ferrocenyl-2-methylinden-1-yl)zirconium dimethyl, rac-dimethylsilanediyl-bis(η 5 (4-ferrocenyl-2-methylinden-1-yl)hafnium dichloride, rac-dimethylsilanediyl-bis(η 5 (4-ferrocenyl-2-methylinden-1-yl)hafnium dimethyl, rac-dimethylsilanediyl-bis(η 5 -2-butyl-4-ferrocenylinden-1-yl)zirconium dichloride, rac-dimethylsilanediyl-bis(η 5 -2-butyl-4-ferrocenylinden-1-yl)zirconium dimethyl, rac-dimethylsilanediyl-bis(η 5 -2-butyl-4-ferrocenylinden-1-yl)hafnium dichloride, rac-dimethylsilanediyl-bis(η 5 (2-butyl-4-ferrocenylinden-1-yl)hafnium dimethyl, rac-dimethylsilanediyl-bis(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)zirconium dichloride, rac-dimethylsilanediyl-bis(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)zirconium dimethyl, rac-dimethylsilanediyl-bis(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)hafnium dichloride, rac-dimethylsilanediyl-bis(η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)hafnium dimethyl, rac-dimethylsilanediyl-bis(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)zirconium dichloride, rac-dimethylsilanediyl-bis(η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)zirconium dimethyl, rac-dimethylsilanediyl-bis(η 5 (4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)hafnium dichloride, and rac-dimethylsilanediyl-bis(η 5 (4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)hafnium dimethyl 12. The catalyst compound of claim 1 or 11 selected from the group consisting of:

20. The catalyst compound of formula (I) or formula (IVa) (dimethylsilanediyl) (η 5 -2-butyl-4-ferrocenylinden-1-yl) (κ 1 (-tert-butylamido)dimethyl titanium, (dimethylsilanediyl) (η 5 -2-butyl-4-ferrocenylinden-1-yl) (κ 1 -tert-butylamido)dimethylzirconium, (dimethylsilanediyl) (η 5 -2-butyl-4-ferrocenylinden-1-yl) (κ 1 -tert-butylamido)dimethylhafnium, (dimethylsilanediyl) (η 5 -2-butyl-4-ferrocenylinden-1-yl) (κ 1 -tert-butylamido)titanium dichloride, (dimethylsilanediyl) (η 5 -2-butyl-4-ferrocenylinden-1-yl) (κ 1 -tert-butylamido)zirconium dichloride, (dimethylsilanediyl) (η 5 -2-butyl-4-ferrocenylinden-1-yl) (κ 1 -tert-butylamido)hafnium dichloride, (dimethylsilanediyl) (η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 (-tert-butylamido)dimethyl titanium, (dimethylsilanediyl) (η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 -tert-butylamido)dimethylzirconium, (dimethylsilanediyl) (η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 -tert-butylamido)dimethylhafnium, (dimethylsilanediyl) (η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 -tert-butylamido)titanium dichloride, (dimethylsilanediyl) (η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 -tert-butylamido)zirconium dichloride, (dimethylsilanediyl) (η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methyl-1H-inden-1-yl)-(κ 1 -tert-butylamido)hafnium dichloride, (dimethylsilanediyl) (η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl) (κ 1 (-tert-butylamido)dimethyl titanium, (dimethylsilanediyl) (η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl) (κ 1 -tert-butylamido)dimethylzirconium, (dimethylsilanediyl) (η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl) (κ 1 -tert-butylamido)dimethylhafnium, (dimethylsilanediyl) (η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl) (κ 1 -tert-butylamido)titanium dichloride, (dimethylsilanediyl) (η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl) (κ 1 -tert-butylamido)zirconium dichloride, and (dimethylsilanediyl) (η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl) (κ 1 (tert-butylamido) hafnium dichloride 14. The catalyst compound of claim 1 or 13 selected from the group consisting of:

21. The catalyst compound of formula (I) or formula (IIIa) Dimethylsilanediyl (η 5 -4-ferrocenyl-2-methylinden-1-yl)(tetramethylcyclopentadienyl)zirconium dichloride, Dimethylsilanediyl (η 5 (4-ferrocenyl-2-methylinden-1-yl)(tetramethylcyclopentadienyl)zirconium dimethyl, Dimethylsilanediyl (η 5 -4-ferrocenyl-2-methylinden-1-yl)(tetramethylcyclopentadienyl)hafnium dichloride, Dimethylsilanediyl (η 5 -4-ferrocenyl-2-methylinden-1-yl)(tetramethylcyclopentadienyl)hafnium dimethyl, Dimethylsilanediyl (η 5 -4-ferrocenyl-2-isopropylinden-1-yl)(tetramethylcyclopentadienyl)zirconium dichloride, Dimethylsilanediyl (η 5 (4-ferrocenyl-2-isopropylinden-1-yl)(tetramethylcyclopentadienyl)zirconium dimethyl, Dimethylsilanediyl (η 5 -4-ferrocenyl-2-isopropylinden-1-yl)(tetramethylcyclopentadienyl)hafnium dichloride, Dimethylsilanediyl (η 5 -4-ferrocenyl-2-isopropylinden-1-yl)(tetramethylcyclopentadienyl)hafnium dimethyl, Dimethylsilanediyl (η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)(tetramethylcyclopentadienyl)zirconium dichloride, Dimethylsilanediyl (η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)(tetramethylcyclopentadienyl)zirconium dimethyl, Dimethylsilanediyl (η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)(tetramethylcyclopentadienyl)hafnium dichloride, Dimethylsilanediyl (η 5 -6-tert-butyl-4-ferrocenyl-5-methoxy-2-methylinden-1-yl)(tetramethylcyclopentadienyl)hafnium dimethyl, Dimethylsilanediyl (η 5 -4-ferrocenyl-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)zirconium dichloride, Dimethylsilanediyl (η 5 -4-ferrocenyl-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)zirconium dimethyl, Dimethylsilanediyl (η 5 -4-ferrocenyl-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)hafnium dichloride, Dimethylsilanediyl (η 5 -4-ferrocenyl-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)hafnium dimethyl, Dimethylsilanediyl (η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)zirconium dichloride, Dimethylsilanediyl (η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)zirconium dimethyl, Dimethylsilanediyl (η 5 -4-ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)hafnium dichloride, and Dimethylsilanediyl (η 5 -4-Ferrocenyl-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tetramethylcyclopentadienyl)hafnium dimethyl 13. The catalyst compound of claim 1 or 12 selected from the group consisting of:

22. A catalyst system comprising an activator and a catalyst compound according to any one of claims 1 to 21.

23. 23. The catalyst system of claim 22 further comprising a support material.

24. The support material is Al 2 O 3 , ZrO 2 , SiO 2 , SiO 2 / Al 2 O 3 , SiO 2 / TiO 2 24. The catalyst system of claim 23, wherein the catalyst is selected from the group consisting of silica clays, silicon oxide / clays, and mixtures thereof.

25. 23. The catalyst system of claim 22, wherein the activator comprises a non-coordinating anion activator.

26. 23. The catalyst system of claim 22, wherein the activator comprises an alkylalumoxane.

27. 1. A process for producing an ethylene alpha-olefin copolymer, comprising: Ethylene and at least one C 3 -C 20 27. The process for producing ethylene and at least one C olefin by introducing alpha-olefins together with the catalyst system of any one of claims 22 to 26 into one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30°C to 230°C. 3 -C 20 polymerizing the alpha-olefin to form an ethylene alpha-olefin copolymer A method comprising:

28. The ethylene alpha-olefin copolymer About 10% to about 35% by weight of C 3 -C 20 comonomer content of alpha-olefin units; and 28. The method of claim 27, wherein the polymer has a z-average molecular weight (Mz) of from about 200,000 g / mol to about 5,000,000 g / mol.

29. 1. A process for producing a propylene homopolymer or a propylene copolymer, comprising: Propylene and optionally comonomers can be produced by introducing propylene and optionally comonomers into one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30°C to 230°C together with the catalyst system of any one of claims 22 to 26. 2 , C 4 -C 20 polymerizing a comonomer selected from the group consisting of alpha-olefins and combinations thereof to form a propylene homopolymer or a propylene copolymer; A method comprising:

30. The catalyst system is about 200,000 g Pmmolcat -1 time -1 ~ about 1,000,000 g Pmmolcat -1 time -1 30. The method of claim 29, wherein the catalytic activity of

31. A propylene homopolymer is produced, and the propylene homopolymer is a z-average molecular weight (Mz) of about 200,000 g / mol to about 800,000 g / mol; a polydispersity index (PDI) value of about 1 to about 3; a melting temperature (Tm) of about 135°C to about 150°C; 30. The method of claim 29, comprising:

32. A propylene homopolymer is produced, and the propylene homopolymer is a mesodivalent element content of about 90% to about 99%; a [mmmm] pentavalent element content of about 80% to about 97%; Less than 125 2,1-position defects per 10,000 propylene units 30. The method of claim 29, comprising:

Images