WO2026024926A1 - Metallocene catalyst compounds for producing polyolefins - Google Patents

Abstract

In some embodiments, a process for producing propylene homopolymer or copolymer includes polymerizing propylene and optionally one or more comonomers selected from the group consisting of one or more C₂ or C₄-C₂₀ alpha-olefins, by introducing the propylene, optionally the one or more C₂ or C₄-C₂₀ alpha-olefins, and optionally hydrogen, with a catalyst system comprising a catalyst compound and an activator, in solution, gas phase, or slurry reactor, in series, or in parallel, at a reactor pressure of about 0.05 MPa to about 1,500 MPa and a reactor temperature of about 30°C to about 230°C to form the propylene homopolymer or copolymer. The catalyst compound is represented by Formula (I) wherein R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently hydrogen or a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group, wherein optionally R⁹ and R¹¹ combine to form a substituted or unsubstituted divalent methylene or divalent ethylene group.

Description

Title: METALLOCENE CATALYST COMPOUNDS FOR PRODUCING POLYOLEFINS INVENTORS: Alexander V. Zabula; Nikola S. Lambic; Torin Dupper; Lubin Luo; JoAnn M. Canich CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of and priority to US Provisional Application No. 63/675,576 filed July 25, 2024, the disclosure of which is incorporated herein by reference. FIELD [0002] The present disclosure relates to ansa-metallocene catalyst compounds, catalyst systems comprising such compounds, and uses thereof. BACKGROUND [0003] Polyolefins are widely used commercially because of their robust physical properties. For example, various types of polyethylenes, including high density, low density, and linear low density polyethylenes, are some of the most commercially useful. Polyolefins are typically prepared with a catalyst that polymerizes olefin monomers. [0004] Catalysts for olefin polymerization typically have transition metals. For example, some catalysts are ansa-metallocenes (also referred to as “bridged” metallocenes), which can be activated by alumoxane or an activator containing a non-coordinating anion. Using these catalysts and catalyst systems, polymerization conditions can be adjusted to provide polyolefins having desired properties. There is interest in finding new metallocene catalysts and catalyst systems that provide polymers having properties, including tunable molecular weights, high activity, and good mechanical properties (e.g., provided by melting point). [0005] In particular, polypropylene (PP) is a polymer that has a large variety of uses. Processes for the manufacture of polypropylene have evolved with improvement in catalyst technology, from complex slurry processes using an inert hydrocarbon diluent, to simpler bulk processes using liquid propylene diluent, to simplified gas phase processes. [0006] However, there remains a need for metallocene catalysts for improved catalyst activity during such polymerizations, particularly for supported metallocene catalysts. Often times, highly active catalyst systems can be used with lower reactor loadings of a catalyst system, however, this makes a catalyst more susceptible to impurities and consequent deactivation. [0007] In addition, regarding end uses of polymers, polymer products used for non-woven fibers should have narrow polydispersity (e.g., to reduce or eliminate fractions of low molecular weight tails to provide improved tensile strength of polypropylene for fiber applications) and have high isotacticity (to provide desired stiffness of polypropylene), but with broad melt flow rate (MFR) capability to provide tailored/improved mechanical properties in the area of both meltblown and spunbound fibers, such as those used in medical applications. In addition to fiber application, additional uses of materials with high and tunable stiffness, narrow polydispersities, and broad melt flow rate (MFR) lie in injection molding, blown and cast film where such properties are desired. [0008] There is a need for new metallocene catalyst compounds and polymerization processes thereof, where the catalyst compounds have high activity and are capable of providing polymers used for medical materials, where the polymers of the polymer products have narrow polydispersity, high isotacticity, and broad melt flow rate (MFR) capability. [0009] References for citing in an Information Disclosure Statement (37 C.F.R.1.97(h)): WO2021/034459-Isotactic Propylene Homopolymers and Copolymers Produced with C1 Symmetric Metallocene Catalysts US2022/0213303-Propylene-Ethylene Random Copolymer WO2022/108973-Metallocene Polypropylene Prepared Using Aromatic Solvent-Free Supports WO2021/194831-Alkylation of Transition Metal Coordination Catalyst Complexes WO2021/247244-Process for Production of Thermoplastic Vulcanizates Using Supported Catalyst Systems and Compositions Made Therefrom US11,236,186B2-Transition Metal Compound for Olefin Polymerization Catalyst, Olefin Polymerization Catalyst Comprising Same, and Polyolefin Polymerized Using Same. SUMMARY [0010] The present disclosure relates to ansa-metallocene catalyst compounds, catalyst systems comprising such compounds, and uses thereof. [0011] In some embodiments, a process for producing propylene homopolymer or copolymer includes polymerizing propylene and optionally one or more comonomers selected from the group consisting of one or more C2 or C4-C20 alpha-olefins, by introducing the propylene, optionally the one or more C2 or C4-C20 alpha-olefins, and optionally hydrogen, with a catalyst system comprising a catalyst compound and an activator, in solution, gas phase, or slurry reactor, in series, or in parallel, at a reactor pressure of about 0.05 MPa to about 1,500 MPa and a reactor temperature of about 30°C to about 230°C to form the propylene homopolymer or copolymer. The catalyst compound is represented by Formula (I):

(I) wherein: M is a group 3 metal, group 4 metal, or group 5 metal; T is a bridging group; each of X¹ and X² is independently a univalent anionic ligand, or X¹ and X² are joined to form a metallocycle ring; R¹, R², R³, and R⁴ are each independently hydrogen or substituted or unsubstituted C₁ to C₆ hydrocarbyl group and, optionally, any adjacent R¹, R², R³ and R⁴ can be joined to form a cyclic structure; R⁵ is a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group; R⁶ and R⁸ are each independently hydrogen or a substituted or unsubstituted C₁ to C20 hydrocarbyl group; R⁷ is a substituted aryl group, an unsubstituted naphthyl group, an unsubstituted anthracenyl group, or a substituted or unsubstituted heteroaryl group; and R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently hydrogen or a substituted or unsubstituted C1 to C20 hydrocarbyl group, wherein optionally R⁹ and R¹¹ combine to form a substituted or unsubstituted divalent methylene, divalent ethylene or divalent hydrocarbyl group. [0012] In some embodiments, a catalyst compound is represented by Formula (IIa) or (IIb):

wherein: M of Formula (IIa) or (IIb) is a group 3 metal, group 4 metal, or group 5 metal; T of Formula (IIa) or (IIb) is a bridging group; each of X¹ and X² of Formula (IIa) or (IIb) is independently a univalent anionic ligand, or X¹ and X² are joined to form a metallocycle ring; R¹, R², R³, and R⁴ of Formula (IIa) or (IIb) are each independently hydrogen or substituted or unsubstituted C₁ to C₆ hydrocarbyl group and, optionally, any adjacent R¹, R², R³ and R⁴ can be joined to form a cyclic structure; R⁵ of Formula (IIa) or (IIb) is a substituted or unsubstituted C1 to C20 hydrocarbyl group; R⁶ and R⁸ of Formula (IIa) or (IIb) are each independently hydrogen or a substituted or unsubstituted C1 to C20 hydrocarbyl group; R⁷ of Formula (IIa) or (IIb) is a substituted aryl group, unsubstituted naphthyl, unsubstituted anthracenyl, or substituted or unsubstituted heteroaryl group; R⁹ and R¹⁰ of Formula (IIa) or (IIb) are each independently hydrogen or a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group; R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently hydrogen or a substituted or unsubstituted C1 to C20 hydrocarbyl group; each instance of R¹¹ and R¹² of Formula (IIa) or (IIb) is independently hydrogen or a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group, and n is 1 or 2 for Formula (IIa) and m is 1 for Formula (IIb). [0013] In some embodiments, a process for producing olefin homopolymer or copolymer includes polymerizing one or more olefins, selected from one or more C₂-C₂₀ alpha-olefins, by introducing the one or more C2-C20 alpha olefins and optionally hydrogen with a catalyst system of the present disclosure, in solution, gas phase or slurry reactor, in series, or in parallel, at a reactor pressure of about 0.05 MPa to about 1,500 MPa, and a reactor temperature of about 30°C to about 230°C to form the alpha olefin homopolymer or copolymer. [0014] In some embodiments, a catalyst compound is represented by Formula (III): wherein: M is a group 3 metal, group 4 metal, or group 5 metal; T is a bridging group; each of X¹ and X² is independently a univalent anionic ligand, or X¹ and X² are joined to form a metallocycle ring; R¹, R², R³, and R⁴ are each independently hydrogen or substituted or unsubstituted C₁ to C6 hydrocarbyl group and, optionally, any adjacent R¹, R², R³ and R⁴ can be joined to form a cyclic structure; R⁵ is a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group; R⁶ and R⁸ are each independently hydrogen or a substituted or unsubstituted C₁ to C20 hydrocarbyl group; R⁷ is a substituted aryl group, an unsubstituted naphthyl group, an unsubstituted anthracenyl group, or a substituted or unsubstituted heteroaryl group; and R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are each independently hydrogen or a substituted or unsubstituted C1 to C20 hydrocarbyl group, wherein optionally R⁹ and R¹¹ combine to form a substituted or unsubstituted divalent methylene, divalent ethylene or divalent hydrocarbyl group; n is an integer of 1, 2 or 3. BRIEF DESCRIPTION OF DRAWINGS [0015] FIG.1 is a graph illustrating flexural modulus measurements as a function of MFR for catalysts I1, I2, and C1-C4. DETAILED DESCRIPTION [0016] The present disclosure relates to ansa-metallocene catalyst compounds, catalyst systems comprising such compounds, and uses thereof. Catalyst compounds of the present disclosure can have high activity. Catalyst compounds can be capable of providing polymers suitable for use in medical materials, where the polymers have narrow polydispersity, high isotacticity, and broad melt flow rate (MFR) capability. [0017] Catalyst compounds of the present disclosure can have 2-substituted 5,6,7,8- tetrahydro-cyclopenta[b]naphthalenyl moieties. Catalyst compounds of the present disclosure can have 2,5,8-substituted-5,6,7,8-tetrahydro-cyclopenta[b]naphthalenyl in combination with a substituted aryl moiety at the 4-position of the 5,6,7,8-tetrahydro-cyclopenta[b]naphthalenyl ring. The substitution at the 5-position combines with the substitution at the 8-position to form a methylene or ethylene bridge. [0018] It has been discovered that catalysts of the present disclosure can exhibit excellent activities, provide high melting points, and have broad molecular weight capabilities particularly for propylene polymerization. Relative to indacenyl and trihydroindacenyl catalyst systems, catalyst compounds of the present disclosure show improvement in in preparation of isotactic polypropylene having high melt temperature and improved stiffness, broad melt flow rate (MFR), and narrow polydispersities. The combination of such polymer properties allows for preparation of polymers applicable in large markets such as hygiene (fibers and injection molding products), rigid and flexible packaging, and automotive applications. [0019] In addition to improved operability, it has been discovered that broad polymer product capability can be achieved. For example, polymers of the present disclosure can have narrow polydispersity, robust isotacticity, and broad MFR capability (provided by broad hydrogen response of the catalyst used for polymerization). High MFR can be provided by high hydrogen loading in the reactor, which catalysts of the present disclosure are amenable to. [0020] Higher activity achieved while maintaining relatively comparable molecular weight capability and narrow polydispersities (PDI) represents a clear advantage of using catalyst systems based on 5,6,7,8-tetrahydro-cyclopenta[b]naphthalenyl groups. Such molecular weight capability range corresponds to a broad MFR range (1 – 1000 MFR), thus significantly extending the applicability of ansa-metallocene catalysts. In addition, catalysts tested were able to maintain narrow MWD while eliminating higher fractions of low molecular weight tails. Such benefit allows for preparation of resins for fiber spinning (spunbound and meltblown) and injection molding articles used in medical applications, which involve cleanliness, narrow polydispersities, low volatile organic compounds (VOCs) and low odor. In addition, high melting points of polypropylenes provided by catalyst compounds of the present disclosure allows for improved stiffness for rigid parts, allowing application of polypropylene for impact copolymer compositions used in automotive industry. For example, polypropylenes of the present disclosure can have reduced defects which provides such improved stiffness (e.g., provided by 5,6,7,8-tetrahydro-cyclopenta[b]naphthalenyl of the catalyst compounds). In addition to improved stiffness, polypropylenes can have significantly improved tensile properties, especially at higher hydrogen loadings (and thus polymer MFR). [0021] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Pr is propyl, iPr is isopropyl, tBu is tert-butyl, Ph is phenyl, OMe is methoxy, PDI is polydispersity index, MWD is molecular weight distribution, MAO is methylalumoxane, SMAO is supported methylalumoxane, NMR is nuclear magnetic resonance, ppm is part per million, THF is tetrahydrofuran. [0022] As used herein, olefin polymerization catalyst(s) refer to any catalyst, such as an organometallic complex or compound that is capable of coordination polymerization addition where successive monomers are added in a monomer chain at the organometallic active center. [0023] The terms “substituent,” “radical,” “group,” and “moiety” may be used interchangeably. [0024] An “olefin,” alternatively referred to as “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 including an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer. A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other. A “terpolymer” is a polymer having three mer units that are different from each other. “Different” is used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers. An "ethylene polymer" or "ethylene copolymer" (both of which are examples of a “polyethylene”) is a polymer or copolymer including at least 50 mol% ethylene derived units. A "propylene polymer" or "propylene copolymer" (both of which are examples of a “polypropylene”) is a polymer or copolymer including at least 50 mol% propylene derived units, and so on. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer including at least 50 mol% ethylene derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer including at least 50 mol% propylene derived units, and so on. [0025] As used herein, “polyethylene” can include “ethylene homopolymer”, “ethylene copolymer”, or combinations thereof. “Polypropylene” can include “propylene homopolymer”, “propylene copolymer”, or combinations thereof. [0026] The term “alpha-olefin” refers to an olefin having a terminal carbon-to-carbon double bond in the structure thereof ((R^”R^’’’)-C=CH2, where R^” and R^’’’ can be independently hydrogen or any hydrocarbyl group; such as R^” is hydrogen and R^’’’ is an alkyl group). A “linear alpha-olefin” is an alpha-olefin defined in this paragraph wherein R^” is hydrogen, and R^’’’ is hydrogen or a linear alkyl group. [0027] For the purposes of the present disclosure, ethylene shall be considered an alpha- olefin. [0028] As used herein, and unless otherwise specified, the term “C_n” means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer. The term “hydrocarbon” means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and or unsaturated), including mixtures of hydrocarbon compounds having different values of n. Likewise, a “Cm-Cy” group or compound refers to a group or compound including carbon atoms at a total number thereof from m to y. Thus, a C₁- C50 alkyl group refers to an alkyl group including carbon atoms at a total number thereof of about 1 to about 50. [0029] Unless otherwise indicated, 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 halide (such as 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, where each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring or chain. [0030] The terms “hydrocarbyl radical,” “hydrocarbyl group,” or “hydrocarbyl” may be used interchangeably and are defined to mean a group including hydrogen and carbon atoms only. For example, a hydrocarbyl can be a C₁-C₁₀₀ radical that may be linear, branched, or cyclic, and when cyclic, 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, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and aryl groups, such as phenyl, benzyl, naphthyl. [0031] The terms “alkoxy” and “alkoxide” mean an alkyl or aryl group bound to an oxygen atom, such as an alkyl ether or aryl ether group/radical connected to an oxygen atom and can include those where the alkyl/aryl group is a C1 to C10 hydrocarbyl. The alkyl group may be straight chain, branched, or cyclic. The alkyl group may be saturated or unsaturated. Examples of suitable alkoxy radicals can include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso- butoxy, sec-butoxy, tert-butoxy, or phenoxyl. [0032] The term "alkenyl" means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more double bonds. These alkenyl radicals may be optionally substituted. Examples of suitable alkenyl radicals can include ethenyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl, including their substituted analogues. [0033] The terms “alkyl radical,” “alkyl group,” and “alkyl” are used interchangeably throughout this disclosure. For purposes of this disclosure, "alkyl radical" is defined to be C₁-C₁₀₀ alkyls that may be linear, branched, or cyclic. Examples of such radicals can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, including their substituted analogues. Some examples of alkyl may 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. [0034] The term "aryl" or "aryl group" means an aromatic ring and the substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, “heteroaryl” means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S. As used herein, the term "aromatic" also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise the term aromatic also refers to substituted aromatics. [0035] For nomenclature purposes, the following numbering schemes are used for cyclopentadienyl, indenyl, fluorenyl, cyclopenta[b]naphthalenyl (also termed benz[e]indenyl), cyclopenta[a]naphthalenyl (also termed benz[f]indenyl), trihydro-s-indacenyl, trihydro-as- indacenyl. The numbering schemes indicate the positions along the ring(s) to which a moiety can be connected. As an example, a moiety such as a phenanthridinyl moiety, can be coupled to the 4-position of an indenyl or a 5,6,7-trihydro-s-indacenyl. It should be noted that indenyl can be considered a cyclopentadienyl with a fused benzene ring. Analogously, fluorenyl can be considered a cyclopentadienyl with two fused benzene rings fused to the cyclopentadienyl ring. Each structure below is drawn and named as an anion.

[0036] Partially hydrogenated polycyclic arenyl ligands retain the numbering scheme of the parent polycyclic arenyl ligand, namely the numbering schemes defined for indenyl, fluorenyl, cyclopenta[b]naphthalenyl, cyclopenta[a]naphthalenyl trihydro-s-indenyl, trihydro-as- indacenyl, tetrahydro-cyclopenta[b]naphthalenyl, tetrahydro-cyclopenta[a]naphthalenyl, pentahydrocyclohepta[f]indenyl, and pentahydrocyclohepta[e]indenyl ligands. [0037] The term “arenyl” ligand is used herein to mean an unsaturated cyclic hydrocarbyl ligand that can consist of one ring, or two or more fused or catenated rings. [0038] As used herein, the term “monocyclic arenyl ligand” is used herein to mean a ^{substituted or unsubstituted monoanionic C} ₅ ^{to C} ₁₀₀ ^{hydrocarbyl ligand that contains an} aromatic five-membered single hydrocarbyl ring structure (also referred to as a cyclopentadienyl ring). [0039] As used herein, the term “polycyclic arenyl ligand” is used herein to mean a ^{substituted or unsubstituted monoanionic C} ₉ ^{to C} ₁₀₃ ^{hydrocarbyl ligand that contains an} aromatic five-membered hydrocarbyl ring (also referred to as a cyclopentadienyl ring) that is 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. Polycyclic arenyl ligands include, but are not limited to indenyl, fluorenyl, cyclopenta[b]naphthalenyl, cyclopenta[a]naphthalenyl tetrahydro-s-indenyl, and tetrahydro-as-indacenyl ligands. [0040] Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl), 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, and tert-butyl). [0041] 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 tetrahydrofuran has five ring atoms. [0042] A heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom substituted ring where a hydrogen on a ring atom is replaced with a heteroatom. For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles may include pyridine, imidazole, and thiazole. [0043] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol. [0044] The terms “catalyst compound”, “catalyst complex”, “transition metal complex”, “transition metal compound”, “precatalyst compound”, and “precatalyst complex” are used interchangeably. [0045] A “catalyst system” is a combination of at least one catalyst compound, at least one activator, an optional coactivator, and an optional support material. When "catalyst system" is used to describe such a pair before activation, it means the unactivated catalyst complex (precatalyst) together with an activator and, optionally, a coactivator. When it is used to describe such a pair after activation, it means the activated complex and the activator or other charge-balancing moiety. The catalyst compound may be neutral as in a precatalyst, or a charged species with a counter ion as in an activated catalyst system. For the purposes of the present disclosure and the claims thereto, when catalyst systems are described as including neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers. A polymerization catalyst system is a catalyst system that can polymerize monomers to polymer. Furthermore, catalyst compounds and activators represented by formulae herein are intended to embrace both neutral and ionic forms of the catalyst compounds and activators. [0046] An “anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion. A “Lewis base” or “neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion. Examples of Lewis bases include ethylether, trimethylamine, pyridine, tetrahydrofuran, dimethylsulfide, and triphenylphosphine. The term “heterocyclic Lewis base” refers to Lewis bases that are also heterocycles. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan. [0047] A scavenger is a compound that can be added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as coactivators. A coactivator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In at least one embodiment, a coactivator can be pre-mixed with the transition metal compound to form an alkylated transition metal compound. [0048] The term "continuous" means a system that operates without interruption or cessation for an extended period of time. For example, a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn. [0049] A solution polymerization means a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends. A solution polymerization can be homogeneous. A homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium. Suitable systems may be not turbid as described in J. Vladimir Oliveira, et al. (2000), “High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems,” Ind. Eng. Chem. Res., v.39, pp. 4627- 4633. [0050] A bulk polymerization means a polymerization process in which the monomers and or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent as a solvent or diluent. A small fraction of inert solvent might be used as a carrier for catalyst and scavenger. A bulk polymerization system contains less than 25 wt% of inert solvent or diluent, such as less than 10 wt%, such as less than 1 wt%, such as 0 wt%. [0051] A polymerization process can include a gas phase polymerization reaction, and in particular a fluidized bed gas phase polymerization reaction. Generally, in a fluidized gas bed process used for producing polymers, a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. In some embodiments, the reaction medium includes condensing agents, which are typically non-coordinating inert liquids that are converted to gas in the polymerization processes, such as isopentane, isohexane, or isobutane. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer. (See, for example, U.S. Pat. Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661; and 5,668,228; all of which are incorporated herein by reference.) The gas-phase polymerization may be carried out in any suitable reactor system, e.g., a stirred- or paddle-type reactor system. See U.S. Pat. Nos. 7,915,357; 8,129,484; 7,202,313; 6,833,417; 6,841,630; 6,989,344; 7,504,463; 7,563,851; and 8,101,691 for discussion of suitable gas phase fluidized bed polymerization systems, which are incorporated herein by reference. [0052] In such polymerization processes, a gas-phase, fluidized-bed process is conducted by passing a stream containing ethylene and an olefin comonomer continuously through a fluidized-bed reactor under reaction conditions and in the presence of a catalyst composition at a velocity sufficient to maintain a bed of solid particles in a suspended state. A stream (which may be called a “cycle gas” stream) containing unreacted ethylene and olefin comonomer is continuously withdrawn from the reactor, compressed, cooled, optionally partially or fully condensed, and recycled back to the reactor. Prepared polyethylene copolymer is withdrawn from the reactor and replacement ethylene and olefin comonomer are added to the recycle stream. In some embodiments, gas inert to the catalyst composition and reactants is present in the gas stream. [0053] The term “single catalyst compound” refers to a catalyst compound corresponding to a single structural formula, although such a catalyst compound may comprise and be used as a mixture of isomers, e.g., stereoisomers. [0054] A catalyst system that utilizes a single catalyst compound means a catalyst system that is prepared using only a single catalyst compound in the preparation of the catalyst system. Thus, such a catalyst system is distinguished from, for example, “dual” catalyst systems, which are prepared using two catalyst compounds having different structural formulas, e.g., the connectivity between the atoms, the number of atoms, and/or the type of atoms in the two catalyst compounds is different. Thus, one catalyst compound is considered different from another if it differs by at least one atom, either by number, type, or connection. 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 to be different catalyst compounds. For example, rac-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethyl and meso-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethyl are considered to be not different. [0055] The terms “cocatalyst” and “activator” are used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation. [0056] Noncoordinating anion (NCA) means an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly. The term NCA is also defined to include multicomponent NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non-coordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group. An NCA coordinates weakly enough that a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center. Any metal or metalloid that can form a compatible, weakly coordinating complex may 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 anion activator includes neutral activators, ionic activators, and Lewis acid activators. The terms “non-coordinating anion activator” and “ionizing activator” are used interchangeably herein. [0057] The terms “process” and “method” are used interchangeably. Catalyst Compounds [0058] This disclosure relates to metallocene catalyst compounds represented by Formula (I): (I) where: M is a group 3 metal (e.g., scandium or yttrium), group 4 metal (e.g., titanium, zirconium, or hafnium), or group 5 metal (e.g., vanadium, niobium, or tantalum); T is a bridging group; each of X¹ and X² is independently a univalent anionic ligand, or X¹ and X² are joined to form a metallocycle ring; R¹, R², R³, and R⁴ are each independently hydrogen or substituted or unsubstituted C1 to C6 hydrocarbyl group and, optionally, any adjacent R¹, R², R³ and R⁴ can be joined to form a cyclic structure; R⁵ is a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group; R⁶ and R⁸ are each independently hydrogen or a substituted or unsubstituted C1 to C₂₀ hydrocarbyl group; R⁷ is a substituted aryl group, an unsubstituted naphthyl group, an unsubstituted anthracenyl group, or a substituted or unsubstituted heteroaryl group; and R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently hydrogen or a substituted or unsubstituted C1 to C20 hydrocarbyl group, wherein optionally R⁹ and R¹¹ combine to form a substituted or unsubstituted divalent methylene, divalent ethylene or divalent hydrocarbyl group. [0059] In some embodiments, R¹, R², R³, and R⁴ are each independently substituted or unsubstituted C1 to C6 hydrocarbyl group. In some embodiments, R¹, R², R³, and R⁴ are each independently selected from methyl, ethyl, propyl, butyl, pentyl, and hexyl. In some embodiments, each of R¹, R², R³, and R⁴ is independently methyl, ethyl, or propyl. In some embodiments, R¹, R², R³, and R⁴ are each methyl. [0060] In some embodiments, R⁵ is an unsubstituted C₁ to C₂₀ hydrocarbyl group. In some embodiments, R⁵ is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. In some embodiments, R⁵ is a primary substituted or unsubstituted C1-C12 alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, isopentyl, neopentyl. In some embodiments, R⁵ is C₁-C₁₀ alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, R⁵ is methyl. [0061] In some embodiments, R⁶ and R⁸ are each independently hydrogen or substituted or unsubstituted C₁ to C₆ hydrocarbyl group. In some embodiments, R⁶ and R⁸ are each independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, and hexyl. In some embodiments, R⁶ and R⁸ are each hydrogen. [0062] In some embodiments, R⁷ is a substituted aryl group represented by the formula: , wherein each of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is independently hydrogen, hydrocarbyl, a heteroatom, or heteroatom-containing group, where at least one of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is not hydrogen, or one or more of R¹⁷ and R¹⁸, R¹⁸ and R¹⁹, R¹⁹ and R²⁰, or R²⁰ and R²¹ are joined to form a completely saturated, partially saturated, or aromatic ring. In some embodiments, each of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is independently hydrogen or C1-C10 alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), where at least one of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is not hydrogen. In some embodiments, each of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is independently hydrogen, methyl, ethyl, isopropyl, tert-butyl, C₁-C₆ alkoxyl, or phenyl, where at least one of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is not hydrogen. In some embodiments, at least one of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is not hydrogen and is an electron donating group. [0063] In some embodiments, R⁷ is selected from: In some embodiments, R⁷ is selected from 1-naphthyl, 2-naphthyl, 9-anthracenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,5-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,6-diethylphenyl, 3,4-diethylphenyl, 3,5-diethylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 3,5-di-isopropylphenyl, 2,5-di- isopropylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 3,5-di-tert- butylphenyl, 3,5-di-tert-butyl-4-methoxy-phenyl, 3,5-di-tert-butyl-4-dimethylamino-phenyl, 2,5-di-tert-butylphenyl, ortho-biphenyl, meta-biphenyl, para-biphenyl, 2-trimethylsilylphenyl, 3-trimethylsilylphenyl, 4-trimethylsilylphenyl, 3,5-bis(trimethylsilyl)phenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, and 3,5-bis(trifluoromethyl)phenyl. In some embodiments, R⁷ is selected from carbazolyl, indolyl, pyrrolyl, or 2-furanyl, 3-furanyl, 5-methyl-2-furanyl, 5-ethyl-2-furanyl, 4,5-dimethyl-2- furanyl, 2-methyl-3-furanyl, 5-methyl-3-furanyl, 2-thiophenyl, 3-thiophenyl, 5-methyl-2- thiophenyl, 2-methyl-3-thiophenyl, and 5-methyl-3-thiophenyl. [0064] In some embodiments, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently hydrogen. In some embodiments, R⁹ and R¹¹ combine to form a substituted or unsubstituted divalent methylene or divalent ethylene group. For example, R⁹ and R¹¹ combine to form a substituted divalent methylene group having one or two substituents, where each substituent of the substituted divalent methylene group is independently an unsubstituted C1 to C₆ hydrocarbyl group. Alternatively, R⁹ and R¹¹ combine to form a substituted divalent ethylene group having one or more substituents (e.g., one, two, three, or four substituents), where each substituent of the substituted divalent ethylene group is independently an unsubstituted C₁ to C₆ hydrocarbyl group. In some embodiments, substitution(s) of a substituted divalent methylene group or a substituted divalent ethylene group are each independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. In some embodiments, substitution(s) of a substituted divalent methylene group or a substituted divalent ethylene group are each independently a substituted or unsubstituted C1-C6 alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, isopentyl, or neopentyl. In some embodiments, substitutions of a substituted divalent methylene group or a substituted divalent ethylene group are each methyl. Alternatively, R⁹ and R¹¹ combine to form an unsubstituted divalent methylene group. Alternatively, R⁹ and R¹¹ combine to form an unsubstituted divalent ethylene group. [0065] In some embodiments, T is represented by the formula R^a ₂J or (R^a)₄J₂ wherein each J is independently C, Si, or Ge, and each R^a is independently hydrogen, halide, a substituted or unsubstituted C₁ to C₄₀ hydrocarbyl, or two R^a can form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted partially saturated ring. In some embodiments, T is represented by the formula R^a2J, (R^a)4J2, or (R^a)6J3 where J is C, Si, or Ge, and each R^a is independently hydrogen or C1 to C20 hydrocarbyl. In some embodiments, two R^a can form a cyclic structure including unsubstituted completely saturated, partially saturated, or aromatic ring. In some embodiments, T is selected from CH2, CH2CH2, C(CH3)2, CPh2, Si(CH3)2, Si(CH2CH3)2, Si(CH2CH2CH3)2, SiPh2, Si(CH3)Ph, Si(CH2)3, Si(CH2)4, or Si(CH2)5. In some embodiments, T is SiMe₂, Si(CH₂CH₃)₂, or Si(CH₂CH₂CH₃)₂. Some examples of suitable bridging groups include 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*, O-O, S-S, R*N-NR*, R*P-PR*, O-S, O-NR*, O-PR*, S-NR*, S-PR*, and R*N-PR* where R* is hydrogen or a C1-C20 containing hydrocarbyl, halocarbyl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R* may join to form a saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. Some examples of the bridging group T include CH₂, CH₂CH₂, SiMe₂, SiPh₂, SiMePh, Si(CH2)3, Si(CH2)4, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me2SiOSiMe2, and PBu. [0066] In some embodiments of Formula (I), M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf). In some embodiments, M is Zr. [0067] In some embodiments, X¹ and X² of Formula (I) are independently selected from a halide or C₁-C₅₀ hydrocarbyl, hydride, amide, alkoxide, sulfide, phosphide, or two of X are joined together to form a metallocycle ring, or X¹ and X² are joined to form a chelating ligand, a diene ligand, or an alkylidene. In some embodiments, X¹ and X² can be independently selected from hydrocarbyl, substituted hydrocarbyl, a heteroatom or heteroatom-containing group such as for example methyl, benzyl, trimethylsilyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamido, diethylamido, dipropylamido, and diisopropylamido. In at least one embodiment, X¹ and X² are each chloro. [0068] In some embodiments of Formula (I), (1) M is Zr or Hf, (2) T is SiMe2, Si(CH2CH3)2, or Si(CH2CH2CH3)2, (3) each of R⁶ and R⁸ is hydrogen or unsubstituted C1-C10 alkyl, (4) each of R⁹, R¹⁰, R¹¹, and R¹² is hydrogen, (5) each of R¹, R², R³, and R⁴ is independently methyl, ethyl, or propyl, (6) R⁵ is C1-C10 alkyl, (7) R⁷ is substituted aryl, and (8) each of X¹ and X² is independently chloro or methyl. [0069] In some embodiments of Formula (I), (1) M is Zr, (2) T is SiMe₂, Si(CH₂CH₃)₂, or Si(CH2CH2CH3)2, (3) each of R⁶ and R⁸ is hydrogen, (4) each of R⁹, R¹⁰, R¹¹, and R¹² is hydrogen, (5) each of R¹, R², R³, and R⁴ is independently methyl or ethyl, (6) R⁵ is C1-C5 alkyl, (7) R⁷ is substituted aryl, and (8) each X¹ and X² is chloro. [0070] In some embodiments of Formula (I), (1) M is Zr, (2) T is SiMe₂, Si(CH₂CH₃)₂, or Si(CH2CH2CH3)2, (3) each of R⁶ and R⁸ is hydrogen, (4) each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ is hydrogen, (5) each of R¹, R², R³, and R⁴ is independently methyl or ethyl, (6) R⁵ is methyl or ethyl, (7) R⁷ is phenyl having one or more substitutions independently selected from tert-butyl, methoxy, and phenyl, and (8) each X¹ and X² is chloro. [0071] In some embodiments of Formula (I), the catalyst is selected from:

[0072] In some embodiments of Formula (I), the catalyst is selected from: [0073] In some embodiments, a metallocene catalyst compound is represented by Formula (IIa) or (IIb): where: M of Formula (IIa) or (IIb) is a group 3 metal (e.g., scandium or yttrium), group 4 metal (e.g., titanium, zirconium, or hafnium), or group 5 metal (e.g., vanadium, niobium, or tantalum); T of Formula (IIa) or (IIb) is a bridging group; each of X¹ and X² of Formula (IIa) or (IIb) is independently a univalent anionic ligand, or X¹ and X² are joined to form a metallocycle ring; R¹, R², R³, and R⁴ of Formula (IIa) or (IIb) are each independently hydrogen or substituted or unsubstituted C1 to C6 hydrocarbyl group and, optionally, any adjacent R¹, R², R³ and R⁴ can be joined to form a cyclic structure; R⁵ of Formula (IIa) or (IIb) is a substituted or unsubstituted C1 to C20 hydrocarbyl group; R⁶ and R⁸ of Formula (IIa) or (IIb) are each independently hydrogen or a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group; R⁷ of Formula (IIa) or (IIb) is a substituted aryl group, unsubstituted naphthyl, unsubstituted anthracenyl, or substituted or unsubstituted heteroaryl group; R⁹ and R¹⁰ of Formula (IIa) or (IIb) are each independently hydrogen or a substituted or unsubstituted C1 to C20 hydrocarbyl group; each instance of R¹¹ and R¹² of Formula (IIa) or (IIb) is independently hydrogen or a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group; R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently hydrogen or a substituted or unsubstituted C1 to C20 hydrocarbyl group; and n is 1 or 2 for Formula (IIa) and m is 1 for Formula (IIb). [0074] In some embodiments, R¹, R², R³, and R⁴ of Formula (IIa) or (IIb) are each independently substituted or unsubstituted C1 to C6 hydrocarbyl group. In some embodiments, R¹, R², R³, and R⁴ are each independently selected from methyl, ethyl, propyl, butyl, pentyl, and hexyl. In some embodiments, each of R¹, R², R³, and R⁴ is independently methyl, ethyl, or propyl. In some embodiments, R¹, R², R³, and R⁴ are each methyl. [0075] In some embodiments, R⁵ of Formula (IIa) or (IIb) is an unsubstituted C1 to C₂₀ hydrocarbyl group. In some embodiments, R⁵ is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. In some embodiments, R⁵ is a primary substituted or unsubstituted C1-C12 alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, isopentyl, neopentyl. In some embodiments, R⁵ is C₁-C₁₀ alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, R⁵ is methyl. [0076] In some embodiments, R⁶ and R⁸ of Formula (IIa) or (IIb) are each independently hydrogen or substituted or unsubstituted C₁ to C₆ hydrocarbyl group. In some embodiments, R⁶ and R⁸ are each independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, and hexyl. In some embodiments, R⁶ and R⁸ of Formula (IIa) or (IIb) are each hydrogen. [0077] In some embodiments, R⁷ of Formula (IIa) or (IIb) is a substituted aryl group represented by the formula: , wherein each of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is independently hydrogen, hydrocarbyl, a heteroatom, or heteroatom-containing group, where at least one of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is not hydrogen, or one or more of R¹⁷ and R¹⁸, R¹⁸ and R¹⁹, R¹⁹ and R²⁰, or R²⁰ and R²¹ are joined to form a completely saturated, partially saturated, or aromatic ring. In some embodiments, each of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is independently hydrogen or C₁-C₁₀ alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), where at least one of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is not hydrogen. In some embodiments, each of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is independently hydrogen, methyl, ethyl, isopropyl, tert-butyl, C1-C6 alkoxyl, or phenyl, where at least one of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is not hydrogen. In some embodiments, at least one of R¹⁷, R¹⁸, R¹⁹, R¹⁹, and R²⁰ is not hydrogen and is an electron donating group. [0078] In some embodiments, R⁷ of Formula (IIa) or (IIb) is selected from: [0079] In some embodiments, R⁷ of Formula (IIa) or (IIb) is selected from 1-naphthyl, 2-naphthyl, 9-anthracenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,5-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,6-diethylphenyl, 3,4-diethylphenyl, 3,5-diethylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 3,5-di-isopropylphenyl, 2,5-di-isopropylphenyl, 2-tert- butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, 3,5-di-tert-butyl- 4-methoxy-phenyl, 3,5-di-tert-butyl-4-dimethylamino-phenyl, 2,5-di-tert-butylphenyl, ortho- biphenyl, meta-biphenyl, para-biphenyl, 2-trimethylsilylphenyl, 3-trimethylsilylphenyl, 4-trimethylsilylphenyl, 3,5-bis(trimethylsilyl)phenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, and 3,5-bis(trifluoromethyl)phenyl. In some embodiments, R⁷ is selected from carbazolyl, indolyl, pyrrolyl, or 2-furanyl, 3-furanyl, 5-methyl-2-furanyl, 5-ethyl-2-furanyl, 4,5-dimethyl-2-furanyl, 2-methyl-3-furanyl, 5-methyl- 3-furanyl, 2-thiophenyl, 3-thiophenyl, 5-methyl-2-thiophenyl, 2-methyl-3-thiophenyl, and 5-methyl-3-thiophenyl. [0080] In some embodiments, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ of Formula (IIa) or (IIb) are each hydrogen. In some embodiments, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, or R¹⁶ of Formula (IIa) or (IIb) are independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. In some embodiments, one or more of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, or R¹⁶ of Formula (IIa) or (IIb) are independently substituted or unsubstituted C1-C6 alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec- butyl, pentyl, isopentyl, or neopentyl. In some embodiments, one or more of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, or R¹⁶ of Formula (IIa) or (IIb) are methyl. [0081] In some embodiments, T of Formula (IIa) or (IIb) is represented by the formula R^a ₂J or (R^a)₄J₂ wherein each J is independently C, Si, or Ge, and each R^a is independently hydrogen, halide, a substituted or unsubstituted C₁ to C₄₀ hydrocarbyl, or two R^a can form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted partially saturated ring. In some embodiments, T is represented by the formula R^a ₂J, (R^a)₄J₂, or (R^a)₆J₃ where J is C, Si, or Ge, and each R^a is independently hydrogen or C1 to C20 hydrocarbyl. In some embodiments, two R^a can form a cyclic structure including unsubstituted completely saturated, partially saturated, or aromatic ring. In some embodiments, T is selected from CH₂, CH2CH2, C(CH3)2, CPh2, Si(CH3)2, Si(CH2CH3)2, Si(CH2CH2CH3)2, SiPh2, Si(CH3)Ph, Si(CH2)3, Si(CH2)4, or Si(CH2)5. In some embodiments, T is SiMe2, Si(CH2CH3)2, or Si(CH₂CH₂CH₃)₂. Some examples of suitable bridging groups include 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*, O-O, S-S, R*N- NR*, R*P-PR*, O-S, O-NR*, O-PR*, S-NR*, S-PR*, and R*N-PR* where R* is hydrogen or a C1-C20 containing hydrocarbyl, halocarbyl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R* may join to form a saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. Some examples of the bridging group T include CH2, CH2CH2, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me₂SiOSiMe₂, and PBu. [0082] In some embodiments of Formula (IIa) or (IIb), M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf). In some embodiments, M is Zr. [0083] In some embodiments, X¹ and X² of Formula (IIa) or (IIb) are independently selected from a halide or C₁-C₅₀ hydrocarbyl, hydride, amide, alkoxide, sulfide, phosphide, or two of X are joined together to form a metallocycle ring, or X¹ and X² are joined to form a chelating ligand, a diene ligand, or an alkylidene. In some embodiments, X¹ and X² can be independently selected from hydrocarbyl, substituted hydrocarbyl, a heteroatom or heteroatom- containing group such as for example methyl, benzyl, trimethylsilyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamido, diethylamido, dipropylamido, and diisopropylamido. In at least one embodiment, X¹ and X² are each chloro. [0084] In some embodiments of Formula (IIa) or (IIb), (1) M is Zr or Hf, (2) T is SiMe₂, Si(CH2CH3)2, or Si(CH2CH2CH3)2, (3) each of R⁶ and R⁸ is hydrogen or unsubstituted C1-C10 alkyl, (4) each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, or R¹⁶ is independently hydrogen or C₁-C₁₀ alkyl, (5) each of R¹, R², R³, and R⁴ is independently methyl, ethyl, or propyl, (6) R⁵ is C₁-C₁₀ alkyl, (7) R⁷ is substituted aryl, and (8) each of X¹ and X² is independently chloro or methyl. [0085] In some embodiments of Formula (IIa) or (IIb), (1) M is Zr, (2) T is SiMe2, Si(CH₂CH₃)₂, or Si(CH₂CH₂CH₃)₂, (3) each of R⁶ and R⁸ is hydrogen, (4) each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, or R¹⁶ is hydrogen, (5) each of R¹, R², R³, and R⁴ is independently methyl or ethyl, (6) R⁵ is C1-C5 alkyl, (7) R⁷ is substituted aryl, and (8) each X¹ and X² is chloro. [0086] In some embodiments of Formula (IIa) or (IIb), (1) M is Zr, (2) T is SiMe₂, Si(CH₂CH₃)₂, or Si(CH₂CH₂CH₃)₂, (3) each of R⁶ and R⁸ is hydrogen, (4) each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, or R¹⁶ is hydrogen, (5) each of R¹, R², R³, and R⁴ is independently methyl or ethyl, (6) R⁵ is methyl or ethyl, (7) R⁷ is phenyl having one or more substitutions independently selected from tert-butyl, methoxy, and phenyl, and (8) each X¹ and X² is chloro. [0087] In some embodiments of Formula (IIa) or (IIb), the catalyst is selected from:

[0088] In some embodiments of Formula (IIa) or (IIb), the catalyst is selected from:

[0089] In some embodiments of Formula (IIa), the catalyst is selected from:

[0090] In some embodiments of Formula (IIa), the catalyst is selected from:

[0091] In at least one embodiment, two or more different catalyst compounds are present in a catalyst system. In at least one embodiment, two or more different catalyst compounds are present in the reaction zone of a reactor where the polymerization process(es) of the present disclosure occur. When two catalyst compounds are used in one reactor as a mixed catalyst system, the two catalyst compounds can be chosen such that the two are compatible. A simple screening method, such as by ¹H or ¹³C NMR, known to those of ordinary skill in the art, can be used to determine which catalyst compounds are compatible. The same activator can be used for both catalyst compounds, however, two different activators, such as a non-coordinating anion activator and an alumoxane, can be used in combination. If one or more catalyst compounds contain an X¹ or X² ligand which is not a hydride, hydrocarbyl, or substituted hydrocarbyl, then the alumoxane may be contacted with the catalyst compound(s) prior to addition of the non-coordinating anion activator. [0092] The two catalyst compounds may be used in any suitable ratio. Molar ratios of (A) transition metal compound to (B) transition metal compound can be (A:B) of 1:1000 to 1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1, alternatively 1:1 to 100:1, alternatively 1:1 to 75:1, and alternatively 5:1 to 50:1. The suitable ratio chosen will depend on the exact catalyst compounds chosen, the method of activation, and the end product desired. In at least one embodiment, when using the two catalyst compounds, where both are activated with the same activator, mole percentages, based upon the molecular weight of the catalyst compounds, can 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, and alternatively about 75% to about 99% A to about 1% to about 10% B. [0093] In some embodiments, a catalyst system includes a catalyst compound of Formula (IIa) and a catalyst compound of Formula (IIb) (for example where n = 1 for each of Formula (IIa) and (IIb)). For example, molar ratios of catalyst compound of Formula (IIb) to catalyst compound of Formula (IIa) can be (IIb):(IIa) of 20:1 to about 20:1, such as about 1:1 to about 10:1, such as about 2:1 to about 6:1, such as about 4:1. [0094] This disclosure relates to metallocene catalyst compounds represented by Formula (III): where: M is a group 3 metal (e.g., scandium or yttrium), group 4 metal (e.g., titanium, zirconium, or hafnium), or group 5 metal (e.g., vanadium, niobium, or tantalum); T is a bridging group; each of X¹ and X² is independently a univalent anionic ligand, or X¹ and X² are joined to form a metallocycle ring; R¹, R², R³, and R⁴ are each independently hydrogen or substituted or unsubstituted C1 to C6 hydrocarbyl group and, optionally, any adjacent R¹, R², R³ and R⁴ can be joined to form a cyclic structure; R⁵ is a substituted or unsubstituted C1 to C20 hydrocarbyl group; R⁶ and R⁸ are each independently hydrogen or a substituted or unsubstituted C1 to C₂₀ hydrocarbyl group; R⁷ is a substituted aryl group, an unsubstituted naphthyl group, an unsubstituted anthracenyl group, or a substituted or unsubstituted heteroaryl group; and R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are each independently hydrogen or a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group, wherein optionally R⁹ and R¹¹ combine to form a substituted or unsubstituted divalent methylene, divalent ethylene or divalent hydrocarbyl group; n is an integer of 1, 2 or 3. [0095] In some embodiments, R¹, R², R³, and R⁴ are each independently substituted or unsubstituted C1 to C6 hydrocarbyl group. In some embodiments, R¹, R², R³, and R⁴ are each independently selected from methyl, ethyl, propyl, butyl, pentyl, and hexyl. In some embodiments, each of R¹, R², R³, and R⁴ is independently methyl, ethyl, or propyl. In some embodiments, R¹, R², R³, and R⁴ are each methyl. [0096] In some embodiments, R⁵ is an unsubstituted C₁ to C₂₀ hydrocarbyl group. In some embodiments, R⁵ is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. In some embodiments, R⁵ is a primary substituted or unsubstituted C₁-C₁₂ alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, isopentyl, neopentyl. In some embodiments, R⁵ is C₁-C₁₀ alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, R⁵ is methyl. [0097] In some embodiments, R⁶ and R⁸ are each independently hydrogen or substituted or unsubstituted C₁ to C₆ hydrocarbyl group. In some embodiments, R⁶ and R⁸ are each independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, and hexyl. In some embodiments, R⁶ and R⁸ are each hydrogen. [0098] In some embodiments, R⁷ is a substituted aryl group represented by the formula: , wherein each of R¹⁹, R²⁰, R²¹, R²², and R²³ is independently hydrogen, hydrocarbyl, a heteroatom, or heteroatom-containing group, where at least one of R¹⁹, R²⁰, R²¹, R²², and R²³ is not hydrogen, or one or more R¹⁹, R²⁰, R²¹, R²², and R²³ are joined to form a completely saturated, partially saturated, or aromatic ring. In some embodiments, each of R¹⁹, R²⁰, R²¹, R²², and R²³ is independently hydrogen or C₁-C₁₀ alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), where at least one of R¹⁹, R²⁰, R²¹, R²², and R²³ is not hydrogen. In some embodiments, each of R¹⁹, R²⁰, R²¹, R²², and R²³ is independently hydrogen, methyl, ethyl, isopropyl, tert-butyl, C₁-C₆ alkoxyl, or phenyl, where at least one of R¹⁹, R²⁰, R²¹, R²², and R²³ is not hydrogen. In some embodiments, at least one of R¹⁹, R²⁰, R²¹, R²², and R²³ is not hydrogen and is an electron donating group. [0099] In some embodiments, R⁷ is selected from: In some embodiments, R⁷ is selected from 1-naphthyl, 2-naphthyl, 9-anthracenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,5-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,6-diethylphenyl, 3,4-diethylphenyl, 3,5-diethylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 3,5-di-isopropylphenyl, 2,5-di- isopropylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 3,5-di-tert- butylphenyl, 3,5-di-tert-butyl-4-methoxy-phenyl, 3,5-di-tert-butyl-4-dimethylamino-phenyl, 2,5-di-tert-butylphenyl, ortho-biphenyl, meta-biphenyl, para-biphenyl, 2-trimethylsilylphenyl, 3-trimethylsilylphenyl, 4-trimethylsilylphenyl, 3,5-bis(trimethylsilyl)phenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, and 3,5-bis(trifluoromethyl)phenyl. In some embodiments, R⁷ is selected from carbazolyl, indolyl, pyrrolyl, or 2-furanyl, 3-furanyl, 5-methyl-2-furanyl, 5-ethyl-2-furanyl, 4,5-dimethyl-2- furanyl, 2-methyl-3-furanyl, 5-methyl-3-furanyl, 2-thiophenyl, 3-thiophenyl, 5-methyl-2- thiophenyl, 2-methyl-3-thiophenyl, and 5-methyl-3-thiophenyl. [0100] In some embodiments, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are each independently hydrogen. In some embodiments, R⁹ and R¹¹ combine to form a substituted or unsubstituted divalent methylene or divalent ethylene group. For example, R⁹ and R¹¹ combine to form a substituted divalent methylene group having one or two substituents, where each substituent of the substituted divalent methylene group is independently an unsubstituted C1 to C₆ hydrocarbyl group. Alternatively, R⁹ and R¹¹ combine to form a substituted divalent ethylene group having one or more substituents (e.g., one, two, three, or four substituents), where each substituent of the substituted divalent ethylene group is independently an unsubstituted C₁ to C₆ hydrocarbyl group. In some embodiments, substitution(s) of a substituted divalent methylene group or a substituted divalent ethylene group are each independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. In some embodiments, substitution(s) of a substituted divalent methylene group or a substituted divalent ethylene group are each independently a substituted or unsubstituted C1-C6 alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, isopentyl, or neopentyl. In some embodiments, substitutions of a substituted divalent methylene group or a substituted divalent ethylene group are each methyl. Alternatively, R⁹ and R¹¹ combine to form an unsubstituted divalent methylene group. Alternatively, R⁹ and R¹¹ combine to form an unsubstituted divalent ethylene group. [0101] In some embodiments, T is represented by the formula R^a ₂J or (R^a)₄J₂ wherein each J is independently C, Si, or Ge, and each R^a is independently hydrogen, halide, a substituted or unsubstituted C1 to C40 hydrocarbyl, or two R^a can form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted partially saturated ring. In some embodiments, T is represented by the formula R^a ₂J, (R^a)₄J₂, or (R^a)₆J₃ where J is C, Si, or Ge, and each R^a is independently hydrogen or C1 to C20 hydrocarbyl. In some embodiments, two R^a can form a cyclic structure including unsubstituted completely saturated, partially saturated, or aromatic ring. In some embodiments, T is selected from CH₂, CH₂CH₂, C(CH₃)₂, CPh₂, Si(CH3)2, Si(CH2CH3)2, Si(CH2CH2CH3)2, SiPh2, Si(CH3)Ph, Si(CH2)3, Si(CH2)4, or Si(CH2)5. In some embodiments, T is SiMe2, Si(CH2CH3)2, or Si(CH2CH2CH3)2. Some examples of suitable bridging groups include 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*, O-O, S-S, R*N-NR*, R*P-PR*, O-S, O-NR*, O-PR*, S- NR*, S-PR*, and R*N-PR* where R* is hydrogen or a C₁-C₂₀ containing hydrocarbyl, halocarbyl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R* may join to form a saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. Some examples of the bridging group T include CH₂, CH₂CH₂, SiMe₂, SiPh₂, SiMePh, Si(CH₂)₃, Si(CH₂)₄, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me₂SiOSiMe₂, and PBu. [0102] In some embodiments of Formula (III), M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf). In some embodiments, M is Zr. [0103] In some embodiments, X¹ and X² of Formula (III) are independently selected from a halide or C1-C50 hydrocarbyl, hydride, amide, alkoxide, sulfide, phosphide, or two of X are joined together to form a metallocycle ring, or X¹ and X² are joined to form a chelating ligand, a diene ligand, or an alkylidene. In some embodiments, X¹ and X² can be independently selected from hydrocarbyl, substituted hydrocarbyl, a heteroatom or heteroatom-containing group such as for example methyl, benzyl, trimethylsilyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamido, diethylamido, dipropylamido, and diisopropylamido. In at least one embodiment, X¹ and X² are each chloro. [0104] In some embodiments of Formula (III), (1) M is Zr or Hf, (2) T is SiMe₂, Si(CH2CH3)2, or Si(CH2CH2CH3)2, (3) each of R⁶ and R⁸ is hydrogen or unsubstituted C1-C10 alkyl, (4) each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ is hydrogen, (5) each of R¹, R², R³, and R⁴ is independently methyl, ethyl, or propyl, (6) R⁵ is C₁-C₁₀ alkyl, (7) R⁷ is substituted aryl, and (8) each of X¹ and X² is independently chloro or methyl. [0105] In some embodiments of Formula (III), (1) M is Zr, (2) T is SiMe2, Si(CH2CH3)2, or Si(CH₂CH₂CH₃)₂, (3) each of R⁶ and R⁸ is hydrogen, (4) each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ is hydrogen, (5) each of R¹, R², R³, and R⁴ is independently methyl or ethyl, (6) R⁵ is C1-C5 alkyl, (7) R⁷ is substituted aryl, and (8) each X¹ and X² is chloro. [0106] In some embodiments of Formula (III), (1) M is Zr, (2) T is SiMe₂, Si(CH₂CH₃)₂, or Si(CH₂CH₂CH₃)₂, (3) each of R⁶ and R⁸ is hydrogen, (4) each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ is hydrogen, (5) each of R¹, R², R³, and R⁴ is independently methyl or ethyl, (6) R⁵ is methyl or ethyl, (7) R⁷ is phenyl having one or more substitutions independently selected from tert-butyl, methoxy, and phenyl, and (8) each X¹ and X² is chloro. [0107] In some embodiments of Formula (III), the catalyst is selected from:

[0108] In some embodiments of Formula (III), the catalyst is selected from:

Methods of Preparing Catalyst Compounds [0109] All air sensitive syntheses are carried out in nitrogen purged dry boxes. All solvents are available from commercial sources. Metallocene complexes can be prepared according to the following general Scheme 1, Scheme 2, or Scheme 3. “R” is a substitution on the aryl ring shown. Scheme 1

Catalyst Systems [0110] In one or more embodiments, the catalyst system of the present disclosure comprises an activator and any of the catalyst compounds described above. While the catalyst systems 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 systems utilize a single catalyst compound corresponding to one of the catalyst compounds of the present disclosure. In yet other embodiments, a catalyst system further includes a support material. In some embodiments, a support material is silica. In some embodiments, the activator includes one or more of alumoxanes, aluminum alkyls, ionizing activators, or combinations thereof. [0111] 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, where the catalyst compound is a single catalyst compound, and the single catalyst compound is the only catalyst compound contacted by an activator in said method. In yet another embodiment, the present disclosure relates to a method of polymerizing olefins comprising contacting at least one olefin with a catalyst system and obtaining a polyolefin. In still another embodiment, the present disclosure relates to a method of 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 embodiments described above, where the catalyst system includes a single catalyst compound. Activators [0112] The terms “cocatalyst” and “activator” are used herein interchangeably. [0113] The catalyst systems described herein may comprise a catalyst complex as described above and an activator such as alumoxane or a non-coordinating anion and may be formed by combining the catalyst compounds described herein with activators in any manner known from the literature including combining them with supports, such as silica. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer). Catalyst systems of the present disclosure may have one or more activators and one, two or more catalyst components. Activators are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral metal compound to a catalytically active metal compound cation. Non-limiting activators, for example, may include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts. Suitable activators may include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, ^-bound, metal ligand making the metal compound cationic and providing a charge-balancing non-coordinating or weakly coordinating anion, e.g., a non-coordinating anion. [0114] In at least one embodiment, the catalyst system includes an activator, a catalyst compound of Formula (I) or Formula (IIa) or Formula (IIb) and optional support. Alumoxane Activators [0115] Alumoxane activators are utilized as activators in the catalyst systems described herein. Alumoxanes are generally oligomeric compounds containing -Al(R^a’’’)-O- sub-units, where 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, such as when the abstractable ligand is an alkyl, halide, alkoxide or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be suitable to use a visually clear methylalumoxane. A 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 a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number US 5,041,584, which is incorporated by reference herein). Another useful alumoxane is solid polymethylaluminoxane as described in US 9,340,630, US 8,404,880, and US 8,975,209, which are incorporated by reference herein. [0116] When the activator is an alumoxane (modified or unmodified), in at least one embodiment, an amount of activator at up to a 5,000-fold molar excess Al/M over the catalyst compound (per metal catalytic site) may be used. The minimum activator-to-catalyst-compound may be a 1:1 molar ratio. Alternate ranges may include about 1:1 to about 500:1, alternately about 1:1 to about 200:1, alternately about 1:1 to about 100:1, or alternately about 1:1 to about 50:1, alternatively about 250:1 to about 500:1. [0117] In an alternate embodiment, little or no alumoxane is used in the polymerization processes described herein. For example, alumoxane can be present at zero mol%, alternately the alumoxane can be present at a molar ratio of aluminum to catalyst compound transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1. Ionizing/Non-Coordinating Anion Activators [0118] The term "non-coordinating anion" (NCA) means an anion which either does not coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a Lewis base. "Compatible" non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion. Non- coordinating anions useful in accordance with the present disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization. Suitable ionizing activators may include an NCA, such as a compatible NCA. [0119] It is within the scope of the present disclosure to use an ionizing activator, neutral or ionic. It is also within the scope of the present disclosure to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators. [0120] For descriptions of some suitable activators please see U.S. Patent Nos.8,658,556 and 6,211,105, incorporated by reference herein. Additional suitable activators are described in U.S. Patent No.11,718,635, incorporated by reference herein. [0121] In some embodiments, an activator can 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. [0122] In at least one embodiment, the activator is selected from one or more of a triaryl carbenium (such as 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). [0123] Suitable activator-to-catalyst ratio, e.g., all NCA activators-to-catalyst ratio may be about a 1:1 molar ratio. Alternate ranges include about 0.1:1 to about 100:1, alternately about 0.5:1 to about 200:1, alternately about 1:1 to about 500:1, alternately about 1:1 to about 1000:1. Suitable ranges can be about 0.5:1 to about 10:1, such as about 1:1 to about 5:1. [0124] It is also within the scope of the present disclosure that the catalyst compounds can be combined with combinations of alumoxanes and NCA's (see for example, US5,153,157; US5,453,410; EP0573120B1; WO1994/007928; and WO1995/014044, incorporated herein by reference, which discuss the use of an alumoxane in combination with an ionizing activator). [0125] Chain transfer agents may be used in polymerization processes of the present disclosure. Useful chain transfer agents can be hydrogen, alkylalumoxanes, a compound represented by the formula AlR₃, ZnR₂ (where each R is, independently, a C₁-C₈ aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyl octyl, or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof. [0126] Furthermore, a catalyst system of the present disclosure may include a metal hydrocarbenyl chain transfer agent represented by the formula: Al(R')_3-v(R'')_v where each R' can be independently a C1-C30 hydrocarbyl group, and or each R'', can be independently a C4-C20 hydrocarbenyl group having an end-vinyl group; and v can be from 0.1 to 3. Alkane-Soluble Activators [0127] Activators of the present disclosure may be those designed to have improved solubility in alkane solvents, such as the activators described in U.S. No. 11,414,436, WO2021/025903, U.S. Pub. No. 2021/0122844, U.S. Pub. No. 2021/0121863, and U.S. No.11584707, incorporated herein by reference. [0128] For example, activators, such as ammonium or phosphonium metallate or metalloid activator compounds, can include (1) ammonium or phosphonium groups and long-chain aliphatic hydrocarbyl groups and (2) metallate or metalloid anions, such as borates or aluminates. [0129] In some embodiments, an activator compound is represented by Formula (AI): [_R ¹ _R ² _R ³ _EH]d ⁺ _[M ^k+ _Qn] ^d- _(AI) wherein: E is nitrogen or phosphorus, such as nitrogen; d is 1, 2 or 3(such as 3); k is 1, 2, or 3(such as 3); n is 1, 2, 3, 4, 5, or 6 (such as 4, 5, or 6); n - k = d (such as d is 1, 2 or 3; k is 3; n is 4, 5, or 6, such as when M is B, n is 4); each of R¹, R², and R³ is independently H, optionally substituted C1-C40 alkyl (such as branched or linear alkyl), or optionally substituted C5-C50-aryl (alternately each of R¹, R², and R³ is independently unsubstituted or substituted with at least one of halide, C₅-C₅₀ aryl, C₆-C₃₅ arylalkyl, C₆-C₃₅ alkylaryl and, in the case of the C₅-C₅₀-aryl, C₁-C₅₀ alkyl); wherein R¹, R², and R³ together comprise 15 or more carbon atoms, M is an element selected from group 13 of the Periodic Table of the Elements, such as B or Al, such as B; and each Q is independently selected from the group consisting of a hydrogen, bridged or unbridged dialkylamido, halide, alkoxy, substituted alkoxy, aryloxy, substituted aryloxy, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted- hydrocarbyl radical, such as a fluorinated aryl group, such fluoro-phenyl or fluoro-naphthyl, such as perfluorophenyl or perfluoronaphthyl. [0130] In some embodiments of activator compounds represented by Formula (AI), at least one of R¹, R², and R³ is a linear or branched C3-C40 alkyl group (alternately such as a linear or branched C₇ to C₄₀ alkyl group). [0131] The present disclosure also provides activator compounds represented by Formula (AI), described above where R¹ is a C1-C30 alkyl group (such as a C1-C10 alkyl group, such as C₁ to C₂ alkyl, such as methyl), wherein R¹ is optionally substituted, and each of R² and R³ is independently an optionally substituted branched or linear C₁-C₄₀ alkyl group or meta and/or para-substituted phenyl group, where the meta and para substituents are, independently, an optionally substituted C1 to C40 hydrocarbyl group, an optionally substituted alkoxy group, an optionally substituted silyl group, a halide, or a halide containing group, wherein R¹, R², and R³ together comprise 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms) and at least one of R¹, R², and R³ is a linear or branched alkyl (such as a C3-C40 branched alkyl, alternately C7-C40 branched alkyl). [0132] The present disclosure further provides catalyst systems including activator compounds represented by Formula (AI), as described above where R¹ is methyl; and each of R² and R³ is independently C1-C40 branched or linear alkyl or C5-C50-aryl, wherein each of R¹, R², and R³ is independently unsubstituted or substituted with at least one of halide, C₅-C₅₀ aryl, C₆-C₃₅ arylalkyl, C₆-C₃₅ alkylaryl and, in the case of the C₅-C₅₀-aryl, C₁-C₅₀ alkyl; wherein R¹, R², and R³ together comprise 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms). [0133] Activator compounds can include one or more of: N,N-di(hydrogenated tallow)methylammonium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-hexadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-tetradecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-dodecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-decyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-octyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-hexyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-butyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-octadecyl-N-decylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate], N-ethyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dihexadecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-ditetradecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-didodecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-didecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dioctylammonium [tetrakis(perfluorophenyl)borate], N-ethyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate], N,N-di(octadecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(hexadecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(tetradecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(dodecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-tetradecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-tetradecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-dodecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-decylanilinium [tetrakis(perfluorophenyl)borate], and N-methyl-N-octylanilinium [tetrakis(perfluorophenyl)borate]. Optional Support Materials [0134] In embodiments herein, the catalyst system may include an inert support material. The supported material can be a porous support material, for example, talc, and inorganic oxides. Other support materials include zeolites, clays, organoclays, or another organic or inorganic support material, or mixtures thereof. [0135] The support material can be an inorganic oxide. The inorganic oxide can be in a finely divided form. Suitable inorganic oxide materials for use in catalyst systems herein may include groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina can be magnesia, titania, zirconia. Other suitable support materials, however, can be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene. Examples of suitable supports may include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania. 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. [0136] The support material, such as an inorganic oxide, can have a surface area of about 2 2 10 m /g to about 700 m /g, pore volume of about 0.1 cm³/g to about 4.0 cm³/g and average particle size of about 5 μm to about 500 μm. The surface area of the support material can be of 2 2 about 50 m /g to about 500 m /g, pore volume of about 0.5 cm³/g to about 3.5 cm³/g and average particle size of about 10 μm to about 200 μm. For example, the surface area of the support 2 2 material can be about 100 m /g to about 400 m /g, pore volume of about 0.8 cm³/g to about 3.0 cm³/g and average particle size can be about 5 μm to about 100 μm. The average pore size of the support material useful in the present disclosure can be of about 10 Å to about 1000 Å, such as about 50 Å to about 500 Å, and such as 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 2 3 m /gm; pore volume of 1.65 cm /gm). For example, suitable silicas can be the silicas marketed under the tradenames of DAVISON™ 952 or DAVISON™ 955 by the Davison Chemical Division of W.R. Grace and Company or PD14024 silica of PQ Corporation or DM-L403 of Asahi Glass Chemical. In other embodiments, PD17062 silica from Ecovyst is used. Alternatively, a silica can be ES-70™ silica (Ecovyst, Malvern, Pennsylvania) that has been calcined, for example (such as at 400°C). [0137] The support material should be dry, that is, free or substantially free of absorbed water. Drying of the support material can be effected by heating or calcining at about 100°C to about 1000°C, such as at least about 600°C. When the support material is silica, it is heated to at least 200°C, such as about 200°C to about 850°C, and such as at about 600°C; and for a time 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 supported catalyst systems of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst including at least one catalyst compound and an activator. [0138] The 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 slurry of the support material is first contacted with the activator for a period of time of about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours at temperatures from -25^oC to about room temperature. The solution of the catalyst compound is then contacted with the isolated support/activator. In alternate embodiments, the slurry of the support material is first contacted with the catalyst compound for a period of time of about 0.5 hour to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. The slurry of the supported catalyst compound is then contacted with the activator solution. [0139] The mixture of the catalyst(s), activator(s) and support is heated about 0°C to about 100°C, such as about 23°C to about 90°C, such as at room temperature. Contact times can be about 0.5 hours to about 24 hours, such as about 2 hours to about 16 hours, or about 4 hours to about 8 hours. [0140] Suitable non-polar solvents are materials in which all of the reactants used herein, e.g., the activator and the catalyst compound, are at least partially soluble and which are liquid at polymerization reaction temperatures. Non-polar solvents can be alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene, may also be employed. [0141] The support, the activator, and at least one catalyst (precursor or pre-catalyst) can be added in any order, e.g., the pre-catalyst can be brought into contact with an activator before contacting the support; or the activator can be brought into contact with a support before contacting at least one pre-catalyst; or at least one pre-catalyst can be brought into contact with a support before contacting an activator. [0142] In at least one embodiment, the support material is a supported methylalumoxane (SMAO), which is an MAO activator treated with silica (e.g., ES-70-875 silica). Polymerization Processes [0143] The present disclosure also relates to polymerization processes where monomer (e.g., ethylene; propylene), and optionally a comonomer, are contacted with a catalyst system including 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 contacting with the monomer. Alternatively, the catalyst compound and activator may be introduced into the polymerization reactor separately, wherein the catalyst compound and activator subsequently react to form the active catalyst. [0144] Monomers may include substituted or unsubstituted C₂ to C₄₀ alpha olefins, such as C₂ to C₂₀ alpha olefins, such as C₂ to C₁₂ alpha olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In at least one embodiment, the monomer includes ethylene and an optional comonomer including one or more C₃ to C₄₀ olefins, such as C₄ to C₂₀ olefins, such as C₆ to C₁₂ olefins. The C₃ to C₄₀ olefin monomers may be linear, branched, or cyclic. The C₃ to C₄₀ cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and or one or more functional groups. In another embodiment, the monomer includes propylene and an optional comonomer including one or more ethylene or C₄ to C₄₀ olefins, such as C₄ to C₂₀ olefins, such as C₆ to C₁₂ olefins. The C₄ to C₄₀ olefin monomers may be linear, branched, or cyclic. The C₄ to C₄₀ cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and or one or more functional groups. [0145] Exemplary C₂ to C₄₀ olefin monomers and optional comonomers may include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, ethylidenenorbornene, vinylnorbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, 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, or dicyclopentadiene. [0146] In some embodiments, a comonomer is selected from ethylene, propylene 1-butene, 1-pentene, 1-hexene, 2-methyl-1-pentene, vinylcyclobutane, 1-heptene, 1-octene, 1-decene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, norbornene, vinylnorbornene, or ethylidine norbornene. [0147] Polymerization processes 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 run in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes can be used. A bulk homogeneous process can be used. Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts found with the monomer; e.g., propane in propylene). In another embodiment, the process is a slurry process (such as, as a gas phase polymerization). As used herein, the term “slurry polymerization process” means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt% of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent). [0148] Suitable diluents/solvents for polymerization may include non-coordinating, inert liquids. Examples of diluents/solvents for polymerization may include straight and branched- chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (e.g., Isopar™); perhalogenated hydrocarbons, such as perfluorinated C₄ to C₁₀ alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents may also include liquid olefins which may 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 are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, such as aromatics are present in the solvent at less than 1 wt%, such as less than 0.5 wt%, such as 0 wt% based upon the weight of the solvents. [0149] In at least one embodiment, a feedstream to the reactor has a feed concentration of the monomers and comonomers for the polymerization is 60 vol% solvent or less, such as 40 vol% or less, such as 20 vol% or less, based on the total volume of the feedstream. In at least one embodiment, the polymerization is run in a bulk process. [0150] Polymerizations can be run at any temperature and or pressure suitable to obtain the desired polymers. Suitable temperatures and or pressures include a temperature of about 0°C to about 300°C, such as about 20°C to about 200°C, such as about 35°C to about 160°C, such as about 80°C to about 160°C, such as about 85°C to about 140°C. Polymerizations can be run at a pressure of about 0.1 MPa to about 25 MPa, such as about 0.45 MPa to about 6 MPa, or about 0.5 MPa to about 4 MPa. [0151] In a suitable polymerization, the run time of the reaction can be up to about 300 minutes, such as about 5 minutes to about 250 minutes, such as about 10 minutes to about 120 minutes, such as about 20 minutes to about 90 minutes, such as 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. [0152] In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 0.001 psig to about 50 psig (0.007 kPa to 345 kPa), such as about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), such as about 0.1 psig to about 10 psig (0.7 kPa to 70 kPa). [0153] In at least one embodiment, the hydrogen content is about 0.0001 ppm to about 2,000 ppm, such as about 0.0001 ppm to about 1,500 ppm, such as about 0.0001 ppm to about 1,000 ppm, such as about 0.0001 ppm to about 500 ppm. Alternately, hydrogen can be present at zero ppm. [0154] In at least one embodiment, little or no alumoxane is used in the process to produce the polymers. For example, alumoxane can be present at zero mol%, alternately the alumoxane can be present at a molar ratio of aluminum to transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1. [0155] Unless otherwise indicated, “catalyst productivity” is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T x W) _{and expressed in units of gPgcat} ^-1 _hr ^-1 _{. Unless otherwise indicated, “catalyst activity” is a} measure of how active the 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 may also be expressed over a period of time T of hours and reported as the mass of product polymer (P) produced per mole or millimole of catalyst (cat) used and expressed in units of gPmmolcat^-1hr^-1. [0156] In at least one embodiment, according to the present disclosure, a catalyst system used for producing propylene homopolymers has a catalyst productivity of greater than 100,000 gPgcat^-1hr^-1, such as greater than 200,000 gPgcat^-1hr^-1, such as greater than 300,000 gPgcat^-1hr^-1, such as about 100,000 gPgcat^-1hr^-1 to about 750,000 gPgcat^-1hr^-1, such as about 100,000 gPgcat^-1hr^-1 to about 200,000 gPgcat^-1hr^-1, alternatively about 200,000 gPgcat^-1hr^-1 to about 300,000 gPgcat^-1hr^-1, alternatively about 300,000 gPgcat^-1hr^-1 to about 400,000 gPgcat^-1hr^-1, alternatively about 400,000 gPgcat^-1hr^-1 to about 500,000 gPgcat^-1hr^-1, alternatively about 500,000 gPgcat^-1hr^-1 to about 600,000 gPgcat^-1hr^-1. [0157] In at least one embodiment, according to the present disclosure, a catalyst system used for producing propylene-ethylene copolymers has a catalyst productivity of greater than 50,000 gPgcat^-1hr^-1, such as greater than 100,000 gPgcat^-1hr^-1, such as greater than 150,000 gPgcat^-1hr^-1, such as about 50,000 gPgcat^-1hr^-1 to about 75,000 gPgcat^-1hr^-1, alternatively about 75,000 gPgcat^-1hr^-1 to about 100,000 gPgcat^-1hr^-1, alternatively about 100,000 gPgcat^-1hr^-1 to about 125,000 gPgcat^-1hr^-1, alternatively about 125,000 gPgcat^-1hr^-1 to about 150,000 gPgcat^-1hr^-1, alternatively about 150,000 gPgcat^-1hr^-1 to about 175,000 gPgcat^-1hr^-1, alternatively about 175,000 gPgcat^-1hr^-1 to about 205,000 gPgcat^-1hr^-1. [0158] In at least one embodiment, according to the present disclosure, a catalyst system used for producing ethylene-octene copolymers has a catalyst productivity of greater than 300,000 gPgcat^-1hr^-1, such as greater than 500,000 gPgcat^-1hr^-1, such as greater than 700,000 gPgcat^-1hr^-1, such as about 300,000 gPgcat^-1hr^-1 to about 900,000 gPgcat^-1hr^-1, such as about 500,000 gPgcat^-1hr^-1 to about 900,000 gPgcat^-1hr^-1, such as about 500,000 gPgcat^-1hr^-1 to about 600,000 gPgcat^-1hr^-1, alternatively about 600,000 gPgcat^-1hr^-1 to about 700,000 gPgcat^-1hr^-1, alternatively about 700,000 gPgcat^-1hr^-1 to about 800,000 gPgcat^-1hr^-1. [0159] In at least one embodiment, the polymerization can be conducted at temperatures from about 50°C to about 80°C at pressures between 2 MPa and 7 MPa in liquid propylene 1) wherein the catalyst system used in the polymerization comprises alumoxane present at a molar ratio of aluminum to transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1; 2) the polymerization occurs in one reaction zone; 3) optionally scavengers (such as trialkyl aluminum compounds) are absent (e.g., present at zero mol%, alternately the scavenger is present at a molar ratio of scavenger to propylene feed is present at 5 to 1000 ppm and, 4) optionally hydrogen is present in the polymerization reactor at a partial pressure of about 0.001 psig to about 50 psig (0.007 kPa to 345 kPa) (such as about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), such as 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 includes no more than one catalyst compound. A "reaction zone", also referred to as a "polymerization zone", is a vessel where polymerization takes place, for example a stirred-tank reactor or a loop reactor. When multiple reactors are used in a continuous polymerization process, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in a batch polymerization process, each polymerization stage is considered as a separate polymerization zone. In at least one embodiment, the polymerization occurs in one reaction zone. Room temperature is 23°C unless otherwise noted. [0160] In an alternate embodiment, the polymerization: 1) can be conducted at temperatures of about 0°C to about 300°C (such as about 25°C to about 250°C, such as about 50°C to about 160°C, such as about 70°C to about 140°C); 2) is conducted at a pressure of atmospheric pressure to about 10 MPa (such as about 0.35 MPa to about 10 MPa, such as about 0.45 MPa to about 6 MPa, such as about 0.5 MPa to about 4 MPa); 3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; such as where aromatics are present in the solvent at less than 1 wt%, such as less than 0.5 wt%, such as at 0 wt% based upon the weight of the solvents); 4) wherein the catalyst system used in the polymerization comprises less than 0.5 mol%, such as about 0 mol% alumoxane, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1; 5) the polymerization occurs in one reaction zone; 6) optionally scavengers (such as trialkyl aluminum compounds) are absent (e.g., present at zero mol%, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, such as less than 50:1, such as less than 15:1, such as less than 10:1); and 7) optionally hydrogen is present in the polymerization reactor at a partial pressure of about 0.001 psig to about 50 psig (0.007 kPa to 345 kPa) (such as about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), such as 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 includes no more than one catalyst compound. [0161] Other additives may also be used in the polymerization, as desired, such as one or more scavengers, hydrogen, aluminum alkyls, or chain transfer agents such as alkylalumoxanes, a compound represented by the formula AlR₃ or ZnR₂ (where each R is, independently, a C1-C8 aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof. Polyolefin Products [0162] The present disclosure also relates to compositions of matter produced by the methods described herein. [0163] In at least one embodiment, a process described herein produces C2 to C20 olefin homopolymers (e.g., ethylene homopolymer; propylene homopolymer), or C2 to C20 olefin copolymers (e.g., ethylene-hexene, ethylene-octene, ethylene-propylene) and or propylene- alpha-olefin copolymers, such as C₃ to C₂₀ copolymers (such as propylene-ethylene, propylene- hexene, or propylene-octene). [0164] In at least one embodiment, the polymers produced herein are homopolymers of ethylene or copolymers of ethylene having, for example, about 0.1 wt% to about 40 wt% (alternately about 5 wt% to about 40 wt%, such as about 10 wt% to about 35 wt%, such as about 10 wt% to about 20 wt%, such as about 10 wt% to about 15 wt%, alternatively about 15 wt% to about 20 wt%, of one or more C₃ to C₂₀ olefin comonomer (such as C₃ to C₁₂ alpha-olefin, such as propylene, butene, hexene, octene, decene, dodecene, such as propylene, butene, hexene, octene). For example, it has been discovered that catalyst compounds of the present disclosure can provide ethylene copolymers having high comonomer content, which can provide improved processability and/or toughness. In at least one embodiment, the monomer is ethylene and the comonomer is hexene or octene, such as about 5 wt% to about 40 wt% hexene or octene, such as about 10 wt% to about 35 wt%, such as about 10 wt% to about 20 wt%, such as about 10 wt% to about 15 wt%, alternatively about 15 wt% to about 20 wt%, based on the weight of the polymer. [0165] In at least one embodiment, the polymers produced herein are homopolymers of propylene or are copolymers of propylene having, for example, about 10 wt% to about 30 wt% (such as about 15 wt% to about 30 wt%, such as about 20 wt% to about 25 wt%suc has about 22 wt% to about 26 wt%, alternatively about 25 wt% to about 30 wt%) of one or more of C2 or C₄ to C₂₀ olefin comonomer (such as ethylene or C₄ to C₁₂ alpha-olefin, such as ethylene, butene, hexene, octene, decene, dodecene, such as ethylene, butene, hexene, octene). In at least one embodiment, the monomer is propylene and the comonomer is ethylene, such as about 10 wt% to about 30 wt% ethylene (such as about 15 wt% to about 30 wt%, such as about 20 wt% to about 25 wt%suc has about 22 wt% to about 26 wt%, alternatively about 25 wt% to about 30 wt%, based on the weight of the polymer. [0166] In at least one embodiment, a polymer produced herein has a unimodal or multimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC). By "unimodal" is meant that the GPC trace has one peak or inflection point. By "multimodal" is meant that the GPC trace has at least two peaks or inflection points. An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versus). [0167] In at least one embodiment, a propylene homopolymer or propylene copolymer of the present disclosure has an Mw about 10,000 g/mol to about 500,000 g/mol, such as about 50,000 g/mol to about 100,000 g/mol, alternatively about 100,000 g/mol to about 150,000 g/mol, such as about 100,000 g/mol to about 125,000 g/mol, alternatively about 150,000 g/mol to about 200,000 g/mol. [0168] In at least one embodiment, a propylene homopolymer or propylene copolymer of the present disclosure has an Mn about 20,000 g/mol to about 1,000,000 g/mol, such as about 100,000 g/mol to about 200,000 g/mol, alternatively about 200,000 g/mol to about 300,000 g/mol, such as about 200,000 g/mol to about 250,000 g/mol, alternatively about 250,000 g/mol to about 300,000 g/mol. [0169] In at least one embodiment, a propylene homopolymer or propylene copolymer of the present disclosure has an Mw/Mn (PDI) value about 1 to about 8, such as about 1.5 to about 4, such as about 1.5 to about 3, such as about 1.5 to about 1.75, alternatively about 1.75 to about 2. [0170] In at least one embodiment, a propylene homopolymer or propylene copolymer of the present disclosure can have a melting point (Tm) (°C) of about 120°C to about 170°C, such as about 145°C to about 165°C, such as about 150°C to about 160°C, such as about 155°C to about 160°C, such as about 157°C to about 159°C. [0171] The stereoregularity of isotactic propylene homopolymers can be determined by the catalyst, total monomer concentrations, and reactor temperature. It is believed that isotactic propylene homopolymers (or copolymers) made according to processes of the present disclosure may comprise up to 99.99% m-dyads based on the total number of dyads present in the polymer, such as a meso dyad (m-dyad) content (m%) of about 85% to about 99.99%, such as about 95% to about 99.95%, such as about 98% to about 99.9%, such as about 99% to about 99.5%, as determined by ¹³C NMR, the remainder balance being r-dyad content (r%). [0172] In some embodiments, an isotactic propylene homopolymer has an [mmmm] pentad content of about 95.0% to about 99.5%, such as about 95.0% to about 98.0%, such as about 95.0% to about 97.0%, as determined by ¹³C NMR. In some embodiments, an isotactic propylene homopolymer has an [rrrr] pentad content of about 0% to about 0.5%, such as about 0.0% to about 0.2%, such as about 0.01% to about 0.1%, as determined by ¹³C NMR. In some embodiments, an isotactic propylene homopolymer has an [mmmr] pentad content of about 0.1% to about 1%, such as about 0.2% to about 0.9%, such as about 0.3% to about 0.9%, as determined by ¹³C NMR. In some embodiments, an isotactic propylene homopolymer has an [rmmr] pentad content of about 0.1% to about 1%, such as about 0.2% to about 0.8%, such as about 0.2% to about 0.7%, as determined by ¹³C NMR. In some embodiments, an isotactic propylene homopolymer has an [mmrr] pentad content of about 0.1% to about 1%, such as about 0.2% to about 0.8%, such as about 0.3% to about 0.7%, as determined by ¹³C NMR. In some embodiments, an isotactic propylene homopolymer has an [mmrm+rmrr] pentad content of about 0.1% to about 1%, such as about 0.2% to about 0.8%, such as about 0.2% to about 0.7%, as determined by ¹³C NMR. In some embodiments, an isotactic propylene homopolymer has an [rmrm] pentad content of about 0.1% to about 1%, such as about 0.1% to about 0.5%, such as about 0.1% to about 0.4%, as determined by ¹³C NMR. In some embodiments, an isotactic propylene homopolymer has an [mrrr] pentad content of about 0% to about 0.5%, such as about 0.3%, as determined by ¹³C NMR. In some embodiments, an isotactic propylene homopolymer has an [mrrm] pentad content of about 0.1% to about 1%, such as about 0.1% to about 0.5%, such as about 0.1% to about 0.3%, as determined by ¹³C NMR. _{[0173] Regio Defect Concentrations by} ¹³ _{Carbon (} ¹³ _{C NMR): NMR spectroscopy is used to measure stereo and regio defect concentrations of polypropylene. NMR spectra are acquired} as described in more detail below. _{[0174] The regio defects each give rise to multiple peaks in the} ¹³ _{Carbon NMR spectrum, and} these are all integrated and averaged (to the extent that they are resolved from other peaks in the spectrum), to improve the measurement accuracy. The chemical shift offsets of the resolvable resonances used in the analysis are tabulated below. The precise peak positions may shift as a function of NMR solvent choice. [0175] The stereo defects measured as “stereo defects/10,000 monomer units” are calculated from the sum of the intensities of mmrr, mmrm+rrmr, and rmrm resonance peaks times 5,000. The intensities used in the calculations 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, 7538-7543. The average meso run length = 10000/[(stereo defects/10000 C) + (2,1-regio defects/10000 C) + (1,3-regio-defects/10000 C)]. [0176] A low amount of regio defects provides a low or eliminated amount of haze of isotactic polypropylene films. It has been discovered that isotactic polypropylenes of the present disclosure can have a low amount of regio defects. In some embodiments, a polypropylene (or copolymer thereof) advantageously has less than 200 regio defects (defined as the sum of 2,1-erythro and 2,1-threo insertions, and 3,1-isomerizations) per 10,000 propylene units, alternatively less than 150, 100, or 50 regio defects per 10,000 propylene units. [0177] In some embodiments, a propylene homopolymer or propylene copolymer advantageously has less than 2002,1-regio defects (defined as the sum of 2,1-erythro and 2,1- threo insertions) per 10,000 propylene units, alternatively less than 100, 50, or 102,1-regio defects per 10,000 propylene units, such as less than 52,1-regio defects per 10,000 propylene units. In some embodiments, a propylene homopolymer or propylene copolymer advantageously has less than 501,3-regio defects (defined as 3,1 insertions/isomerizations) per 10,000 propylene units, such as less than 10, 5 or 2 and such as zero 1,3-regio defects per 10,000 propylene units. [0178] In some embodiments, a propylene homopolymer or propylene copolymer has less than 500 stereo defects per 10,000 propylene units, alternatively greater than 5, 15 or 30 and less than 100 or 85 stereo defects per 10,000 propylene units. In some embodiments, a propylene homopolymer has an average meso run length of about 20 to about 140, such as about 50 to about 130, such as about 80 to about 100 or about 100 to about 120. [0179] In some embodiments, a propylene homopolymer or propylene copolymer has a flexural modulus of less than or equal to about 2000 MPa, such as less than or equal to about 1800 MPa, such as less than or equal to about 1600 MPa, such as about 1100 MPa to about 1800 MPa, such as about 1400 MPa to about 1600 MPa, such as about 1400 MPa to 1500 MPa, alternatively about 1500 MPa to about 1600 MPa, when determined according to ASTM D790. [0180] In some embodiments, a polyolefin of the present disclosure has a melt flow rate or mass flow rate (MFR of about 0.01 g/10min to about 2000 g/10min, such as about 0.05 to about 1000 g/10min, such as about 0.1 to about 500 g/10min, such as about 0.5 to 100g/10min, such as about 2-50g/10min, as measured according to ASTM D1238 and ISO 1133. GPC 4-D [0181] Unless otherwise indicated, the distribution and the moments of molecular weight (Mw, Mn, Mz, Mw/Mn, etc.), the comonomer content, and the branching index (g') are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC- IR) equipped with a multiple-channel band-filter based Infrared detector IR5 with a multiple- channel band filter based infrared detector ensemble IR5 with band region covering from about 2700 cm^-1 to about 3000 cm^-1 (representing saturated C-H stretching vibration), an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-µm Mixed-B LS columns are used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) comprising ~300 ppm antioxidant BHT can be used as the mobile phase at a nominal flow rate of ~1.0 mL/min and a nominal injection volume of ~200 μL. The whole system including transfer lines, columns, and detectors can be contained in an oven maintained at ~145°C. A given amount of sample can be weighed and sealed in a standard vial with ~10 μL flow marker (heptane) added thereto. After loading the vial in the auto-sampler, the oligomer or polymer may automatically be dissolved in the instrument with ~8 mL added TCB solvent at ~160°C with continuous shaking. The sample solution concentration can be from ~0.2 to ~2.0 mg/ml, with lower concentrations 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 with polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm/mole. The MW at each elution volume is calculated with following equation: log log^^ൌ where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, αPS = 0.67 and KPS = 0.000175, α and K for other materials are as calculated and published in literature (Sun, T. et al. (2001) Macromolecules, v.34, pg.6812), except that for purposes of this present disclosure and claims thereto, ^ = 0.705 and K = 0.0000229 for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, ^ = 0.695 and K = 0.000579 for linear ethylene polymers, ^ = 0.705 and K = 0.0002288 for linear propylene polymers, and ^ = 0.695 and K = 0.000181 for linear butene polymers. Concentrations are expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity (hence K in the Mark–Houwink equation) is expressed in dL/g unless otherwise noted. [0182] The comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH2 and CH3 channel calibrated with a series of PE and PP homo/copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, 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 computed as a function of molecular weight by applying a chain-end correction to the CH3/1000TC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % comonomer is then obtained from the following expression in which ^^ is 0.3, 0.4, 0.6, 0.8, and so on for C₃, C₄, C₆, C₈, and so on co-monomers, respectively: ^_{^2 ൌ ^^ ∗ SCB/1000TC .} [0183] The bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the entire signals of the CH₃ and CH₂ channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained B_{ulk IR ratio ൌ} Area of CH₃ signal within integration limits Area of CH₂ signal within integration limits . [0184] Then the same calibration of the CH₃ and CH₂ signal ratio, as mentioned previously in obtaining the CH3/1000TC as a function of molecular weight, is applied to obtain the bulk CH3/1000TC. A bulk methyl chain ends per 1000TC (bulk CH3end/1000TC) is obtained by weight-averaging the chain-end correction over the molecular-weight range. Then ^_{^2^^ ൌ ^^ ∗ bulk CH3/1000TC bulk SCB/1000TC ൌ bulk CH3/1000TC െ bulk CH3end/1000TC} and bulk SCB/1000TC is converted to bulk ^^2 in the same manner as described above. [0185] The LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII. 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, M. B., Ed.; Academic Press, 1972.): [0186] Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle ^, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial ^{coefficient, P(θ) is the form factor for a monodisperse random coil, and K} _o ^{is the optical} constant for the system: where N_A is Avogadro’s number, and (dn/dc) is the refractive index increment for the system. The refractive index, n = 1.500 for TCB at 145°C and λ = 665 nm. For analyzing polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn/dc = 0.1048 ml/mg and A2 = 0.0015; for analyzing ethylene-butene copolymers, dn/dc = 0.1048*(1-0.00126*w2) ml/mg and A₂ = 0.0015 where w2 is weight percent butene comonomer. [0187] A high temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential ^{pressure. The specific viscosity, η} _s ^{, for the solution flowing through the viscometer is} calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the equation [η]= η_s/c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as_{M ^ K PSM^ PS ^1 [ ^ ] , where ^ps is 0.67 and Kps is 0.000175.} ^{[0188] The branching index (g'} _vis ^{) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, [η]} _avg ^{, of the sample is calculated by:} where the summations are over the chromatographic slices, i, between the integration limits. ^{The branching index g'} _vis ^{is defined as: where M} _v ^{is the viscosity-average molecular weight based on molecular weights determined} by LS analysis and the K and ^ are for the reference linear polymer, which are, for purposes of this present disclosure and claims thereto, ^ = 0.705 and K = 0.0000229 for ethylene- propylene copolymers and ethylene-propylene-diene terpolymers, ^ = 0.695 and K = 0.000579 for linear ethylene polymers, ^ = 0.705 and K = 0.0002288 for linear propylene polymers, ^ = 0.695 and K = 0.000181 for linear butene polymers. Concentrations are expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g unless otherwise noted. Calculation of the w2b values is as discussed above. Blends [0189] In some embodiments, the polymer (such as the polyethylene, polypropylene, or copolymers thereof) produced herein is combined with one or more additional polymers prior to being formed into a film, molded part or other article. Other useful polymers include polyethylene, isotactic polypropylene, syndiotactic polypropylene, random copolymer 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, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, 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, polyacetal, polyvinylidine fluoride, polyethylene glycols, and or polyisobutylene. [0190] In at least one embodiment, the polymer (such as the polyethylene, polypropylene) is present in the above blends, at about 10 wt% to about 99 wt%, based upon the weight of the polymers in the blend, such as about 20 wt% to about 95 wt%, such as at least about 30 wt% to about 90 wt%, such as at least about 40 wt% to about 90 wt%, such as at least about 50 wt% to about 90 wt%, such as at least about 60 wt% to about 90 wt%, such as at least about 70 to about 90 wt%. [0191] Additionally, additives may be included in the blend, in one or more components of the blend, and or in a product formed from the blend, such as a film, as desired. Such additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX^TM 1010 or IRGANOX^TM 1076 available from Ciba-Geigy); phosphites (e.g., IRGAFOS^TM 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; fillers; talc. Films [0192] Any of the foregoing polymers, or blends thereof, may be used in a variety of end- use applications. Such applications include, for example, mono- or multi-layer blown, extruded, and or shrink films. These films may be formed by any number of well-known extrusion or coextrusion techniques, such as a blown bubble film processing technique, wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uni-axial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film. Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents. One or more of the layers of the film may be oriented in the transverse and or longitudinal directions to the same or different extents. The uniaxially orientation can be accomplished using suitable cold drawing or hot drawing methods. Biaxial orientation can be accomplished using tenter frame equipment or a double bubble processes and may occur before or after the individual layers are brought together. For example, an ethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented. Likewise, oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further. However, in another embodiment the film is oriented to the same extent in both the MD and TD directions. [0193] The films may vary in thickness depending on the intended application; however, films of a thickness of about 1 μm to about 50 μm can be suitable. Films intended for packaging can be about 10 μm to about 50 μm thick. The thickness of the sealing layer can be about 0.2 μm to about 50 μm. There may be a sealing layer on both the inner and outer surfaces of the film or the sealing layer may be present on only the inner or the outer surface. EXPERIMENTAL [0194] The experimental methods and analytical techniques utilized in Examples below are described in this section. [0195] Highly active C1-symmetric Zr-catalysts were synthesized having the aryl substituted 5,6,7,8-tetrahydro-cyclopenta[b]naphthalenyl (I1-I3), 5-tetracyclo[9.2.2.02,10.04,8]pentadeca-2,4(8),6,9-tetraenyl] (I4 and I5), tetracyclo[9.2.1.02,10.04,8]tetradeca-2,4(8),6,9-tetraenyl] (I6) or 5,6,7,8,9- pentahydrocyclohepta[f]indene (I7 and I8) cores (Scheme 4) for olefin polymerization yielding potentially marketable products. In addition to high activity, polypropylenes prepared with inventive catalysts demonstrate improved stiffness, high melting points, broad hydrogen response and narrow polydispersities. The combination of such features allows for preparation of resins especially applicable in large market segments such as hygiene (fibers and injection molding products), rigid and flexible packaging, and automotive. [0196] New catalysts were prepared using a multi-step synthesis described herein. Catalysts I1-I8 were tested using high-throughput polymerization in parallel pressure reactors for ethylene, propylene and for copolymerizing ethylene/propylene and ethylene/1-octene mixtures. The activities, observed in high-throughput experimentation, are comparable to the most active C1-symmetric metallocenes (C1-C4). The corresponding results are summarized in Tables 1-3.

Scheme 4: I1-I8 catalysts and comparative C1-C4 catalysts [0197] High-throughput screening for propylene polymerization showed that the activity for I1 and I2 is comparable to C1 and C2 and even exceeds the performance of C3 and C4 catalysts (Table 1). The invented catalysts produce isotactic polypropylene with more regular microstructure compared to C1-C4: total number of defects, identified by NMR spectroscopy, is lower in the product obtained by invented catalysts than by C1-C4 (>=104). It results in the noticeably higher Tm for polypropylene (158.72°C for I1 vs 157.16°C for C1). For ethylene/propylene copolymerization the activity for I1 is lower than that observed for C1 and C2 but higher than the activity of C3 and C4 (Table 2). The activity for I2 is comparable to C1 and C2. Interestingly, the catalysts I1-I3 are capable of producing EP resins with higher Mw’s compared to C1-C3. Table 1. Propylene solution polymerization data for I1-I8 and C1-C4 in PPR (1 g propylene, 0.03 ^mol catalyst, MAO/catalyst ratio 500, 70 ^oC, isohexane). Each value is an average of at least 3 runs. Table 2. Propylene/ethylene solution copolymerization data for I1-I8 and C1-C4 (1 g propylene, 0.02 ^mol catalyst, MAO/catalyst ratio 500, 60 psi ethylene, 70°C, isohexane). Each value is an average of 3 runs. [0198] Catalysts I1 and I2 demonstrate a better performance for ethylene/1-octene copolymerization compared to catalyst C1 (Table 3). Moreover, the activity for I1 and I2 increases in the presence of 1-octene in contrast to a noticeable reduction of the activity for copolymerization observed for C1. Table 3. Ethylene/1-octene solution copolymerization data for I1, I2 and C1 (0.02 ^mol catalyst, MAO/catalyst ratio 500, 115 psi ethylene, 85°C, isohexane). Each value is an average of 2 runs. [0199] In order to illustrate the performance of new catalysts in slurry polymerization – catalysts I1-I4 and comparative examples C1-C3 were supported using silica supported MAO (sMAO) and tested under industrially relevant propylene polymerization conditions at 70°C. The corresponding results are summarized in Table 4. Novel catalysts I1 and I2 reproducibly demonstrate high melting point for the obtained polypropylene. Thus, there is a clear advantage of invented catalysts for the production of isotactic polypropylene. In addition, the Tm of the obtained polypropylene is around 160°C that allows applications in impact copolymers. Table 4. Propylene polymerization data for I1-I4, C1-C4 in 2L reactor.

Mechanical properties of polypropylenes [0200] Mechanical testing of samples prepared with inventive catalysts I1 and I2 was compared against analogous samples prepared with catalysts C1-C4. The samples were compounded with 500 ppm Irganox 1010 and 500 ppm Irgaphos 168 during melt extrusion, followed by injection molding of type 3 bars. [0201] In the base case, catalysts I1 and I2 showed generally improved stiffness compared to catalysts C3 and C4 across the wide MFR range. The origin behind this lies in the higher melting points of polymers prepared with catalysts I1 and I2 (Table 4, Figure 1). Comparing samples prepared with I1 with analogous samples of catalyst C1 show comparable stiffness at low MFR. However, in the injection molding regime of MFR, sample with MFR=36 of catalyst I1 showed flexural modulus of 1454 MPa, which is significantly improved compared to sample at MFR=42 prepared with catalyst C1 (flexural modulus = 1232 MPa). A similar trend has been observed with catalyst I2, where remarkably high stiffness can be achieved across the broad MFR range. For example, at MFR=33 and MFR=94, catalyst I2 delivered polymers with flexural modulus of ~1600 MPa. Analogous catalyst C2 delivered polymers of lower stiffness (1445 MPa and 1243 MPa). In addition, polymers prepared with catalyst I2 demonstrate very low dependence of stiffness on MFR. [0202] FIG.1 is a graph illustrating flexural modulus measurements as a function of MFR for catalysts I1, I2 and C1-C4. [0203] NMR Studies: Polypropylene microstructure is determined by ¹³C-NMR spectroscopy, including the concentration of isotactic and syndiotactic diads ([m] and [r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). The designation “m” or “r” describes the stereochemistry of pairs of contiguous propylene groups, “m” referring to meso and “r” to racemic. Samples are dissolved in d2-1,1,2,2-tetrachloroethane, and spectra recorded at 120°C using a ¹³C frequency of 125 MHz (or higher) NMR spectrometer. Polymer resonance peaks are referenced to mmmm = 21.83 ppm. Calculations involved in the characterization of polymers by NMR are described by F. A. Bovey in Polymer Conformation and Configuration (Academic Press, New York 1969) and J. Randall in Polymer Sequence Determination, ¹³C-NMR Method (Academic Press, New York, 1977). Syntheses of Catalysts I1-I3. [0204] 4-Bromo-2-methyl-2,3,5,6,7,8-hexahydro-1H-cyclopenta[b]naphthalen-1-one. Under the nitrogen atmosphere, a cold solution (0°C) of 2-methyl-2,3,5,6,7,8-hexahydro-1H- cyclopenta[b]naphthalen-1-one (1.58 g, 7.89 mmol, prepared according to US 11,236,186 B2) in CH₂Cl₂ (30 mL) was slowly added under stirring to the solution of AlBr₃ (5.83 g, 21.9 mmol) in CH2Cl2 (30 mL) at 0°C. The resulting mixture was stirred for 1 hour at 0°C before the solution of Br2 (1.26 g, 7.89 mmol) in CH2Cl2 (30 mL) was added over 45 minutes at 0°C. The temperature of the reaction mixture was gradually increased to 25°C and the mixture was stirred for 6 hours. Then, the obtained mixture was poured into ice water (100 mL), and the formed organic layer was separated. The aqueous layer was extracted with CH2Cl2 (2 x 30 mL) and the combined organic layer was subsequently washed with Na₂CO₃ (50 mL), water (3 x 100 mL), and brine (2 x 50 mL). The combined organic layer was then dried over MgSO4, filtered and evaporated to give an orange oily product. The product was dissolved in the CH2Cl2/n-hexane mixture (1:1, v:v) and passed through a short silica gel plug. The evaporation of solvents afforded a yellow oil, slowly crystallizing into a yellowish solid. Yield: 2.07 g, 94%. ¹H NMR (400 MHz, CDCl3): δ 7.47 (s, Ar-H), 3.34 (m, 1H), 2.86 (m, 4H), 2.74 (m, 1H), 2.67-2.61 (m, 1H), 1.89-1.80 (m, 4H), 1.33 (d, 3H). [0205] 9-Bromo-2-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene Solid sodium borohydride (0.95 g, 25.1 mmol) was added to a pre-cooled, stirring suspension of 4-bromo-2-methyl-2,3,5,6,7,8-hexahydro-1H-cyclopenta[b]naphthalen-1-one (7.00 g, 25.1 mmol) in methanol (50 mL) at 0°C. The reaction mixture was then stirred at room temperature for 2 hours before being concentrated to ca 1/2 of the initial volume. Then, aqueous hydrochloric acid (1M, 100 mL) and diethyl ether (100 mL) were added. The obtained aqueous layer was separated, and the remaining organic phase was subsequently washed with aqueous hydrochloric acid (1M, 50 mL), water (50 mL), and brine (50 mL), and finally dried over anhydrous MgSO4. Evaporation of the solvent afforded a white solid product which was used for the next step without any purification. This intermediate product and catalytic amount of p-toluenesulfonic acid monohydrate (70 mg, 0.365 mmol) were dissolved in toluene (50 mL) and the obtained mixture was refluxed for 90 minutes. Then, the reaction mixture was transferred into a separatory funnel with water (200 mL), extracting further from the reaction flask with toluene (40 mL). The aqueous layer was separated, and the toluene phase was washed with brine. Drying over anhydrous MgSO₄ and evaporation of toluene gave a crude product which was purified by passing through a short silica plug using n-hexane/CH2Cl2 (3:1, v:v) as an eluent. The product was isolated as a beige solid after evaporation of solvents. Overall yield over two steps: 6.30 g, 96%. ¹H NMR (400 MHz, CDCl₃) δ 7.35 (s, 1H, Ar-H), 6.41 (m, 1H), 3.10 (s, 2H), 2.80 (t, 2H), 2.72 (t, 2H), 2.18 (s, 3H), 1.84 (m, 4H).¹³C NMR (101 MHz, CDCl3) δ 146.15, 144.25, 140.91, 134.04, 131.04, 126.26, 123.77, 121.33, 41.16, 30.35, 27.29, 23.57, 22.61, 16.83. [0206] 9-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-1H- cyclopenta[b]naphthalene A 500 mL pressure-resistant flask was charged under nitrogen atmosphere with 9-bromo-2- methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene (4.80 g, 18.2 mmol), (3,5-di-tert- butyl-4-methoxyphenyl)boronic acid (4.95 g, 20.1 mmol), K2CO3 (5.55 g, 40.1 mmol), bis(dibenzylideneacetone)palladium(0) (0.524 g, 0.912 mmol), 1,3,5,7-tetramethyl-6-phenyl- 2,4,8-trioxa-6-phosphaadamantane (0.800 g, 2.74 mmol) and THF (200 mL) followed by degassed water (25 mL). The flask was sealed and heated with vigorous stirring at 80°C for 16 hours. Then, the flask was cooled to the ambient temperature and the reaction volume was reduced to ca 30 mL. The product was extracted into diethylether (3 ^ 50 mL) and the combined organic phase was subsequently washed with water (2 ^ 75 mL), saturated sodium carbonate solution (2 ^ 75 mL) and brine (2 ^ 75 mL). The obtained organic phase was dried over MgSO4 and evaporated to give 9.3 g of the crude product. The product was purified on Biotage automated column using silica gel and the mixture of dichrolomethane and n-hexane (5:95, v:v, respectively) as an eluent. Yield: 6.27 g, 85%. ¹H NMR (400 MHz, CDCl3): δ 7.17 (s, 2H), 7.05 (s, 1H), 6.50 (s, 1H), 3.81 (s, 3H, OCH3), 3.08 (s, 2H), 2.93 (t, J = 6.3 Hz, 2H), 2.54 (t, J = 6.2 Hz, 2H), 2.13 (s, 3H), 1.88–1.76 (m, 4H), 1.51 (s, 18H, tBu). ¹³C NMR (101 MHz, CDCl₃): δ 157.92, 145.84, 143.13, 143.04, 140.09, 138.20, 135.51, 134.44, 130.35, 127.26, 126.78, 119.40, 64.18, 42.60, 35.90, 32.36, 30.46, 28.06, 23.83, 23.22, 16.86. [0207] 9-(4-(Tert-butyl)phenyl)-2-methyl-5,6,7,8-tetrahydro-1H- cyclopenta[b]naphthalene An 100 mL pressure-resistant flask was charged under nitrogen atmosphere with 9-bromo-2- methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene (0.99 g, 3.76 mmol), 4-tert- butylphenylboronic acid (0.67 g, 3.76 mmol), K₂CO₃ (1.16 g, 8.28 mmol), bis(dibenzylideneacetone)palladium(0) (21.6 mg, 0.038 mmol), 1,3,5,7-tetramethyl-6-phenyl- 2,4,8-trioxa-6-phosphaadamantane (33 mg, 0.113 mmol) and THF (20 mL) followed by degassed water (3 mL). The flask was sealed and heated with vigorous stirring at 75°C for 12 hours. Then, the flask was cooled to the ambient temperature and THF was evaporated. The product was extracted into n-hexane (2 ^ 50 mL) and the combined organic phase was subsequently washed with water (2 ^ 50 mL), saturated sodium carbonate solution (2 ^ 50 mL) and brine (2 ^ 50 mL). The obtained organic phase was dried over MgSO4 and evaporated to give a crude product as a brown oil. The product was purified by dissolving in n-hexane/dichloromethane (3:1, v:v. respectively) and passing the resulting solution through a short silica plug. Evaporation of solvent and drying the product at 55°C in vacuo afforded a colorless solid. Yield: 1.14 g, 96%. ¹H NMR (400 MHz, CDCl₃): δ 7.44 (d, J = 8.3 Hz, 2H), 7.29 (d, J = 8.3 Hz, 2H), 7.05 (s, 1H), 6.49 (s, 1H), 3.21 (s, 2H), 2.83 (t, J = 6.5 Hz, 2H), 2.68 (t, J = 6.2 Hz, 2H), 2.20 (s, 3H), 1.91–1.83 (m, 2H), 1.83–1.74 (m, 2H), 1.40 (s, 9H). ¹³C NMR (101 MHz, CDCl₃): δ 149.15, 145.15, 142.69, 140.85, 140.50, 139.82, 131.97, 130.24, 129.06, 126.99, 124.76, 119.15, 41.44, 34.51, 31.47, 28.63, 27.09, 23.72, 22.90, 16.87. [0208] 9-([1,1'-biphenyl]-2-yl)-2-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene An 100 mL pressure-resistant flask was charged under nitrogen atmosphere with 9-bromo-2- methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene (0.62 g, 2.37 mmol), [1,1'-biphenyl]- 2-ylboronic acid (0.51 g, 2.57 mmol), K₂CO₃ (0.71 g, 5.14 mmol), bis(dibenzylideneacetone)palladium(0) (67 mg, 0.117 mmol), 1,3,5,7-tetramethyl-6-phenyl- 2,4,8-trioxa-6-phosphaadamantane (102 mg, 0.351 mmol) and THF (30 mL) followed by degassed water (4 mL). The flask was sealed and heated with vigorous stirring at 75°C for 60 hours. Then, the flask was cooled to the ambient temperature and THF was evaporated. The product was extracted into n-hexane (3 ^ 50 mL) and the combined organic phase was subsequently washed with water (3 ^ 50 mL), saturated sodium carbonate solution (2 ^ 50 mL) and brine (2 ^ 50 mL). The obtained organic phase was dried over MgSO4 and evaporated to give a crude product as an orange oil. The product was dissolved in n-hexane/dichloromethane (3:1, v:v. respectively) and the resulting solution was passed through a short silica plug. The solvent was evaporated and the product was further purified on Biotage automated column using the mixture of ethyl acetate and n-hexane (1:9; v:v, respectively) as an eluent and silica gel to give a colorless solid. Yield: 0.65 g, 83%. ¹H NMR (500 MHz, CDCl3): δ 7.53 (dd, J = 7.6, 1.6 Hz, 1H), 7.47 (td, J = 7.5, 1.5 Hz, 1H), 7.43 (td, J = 7.4, 1.5 Hz, 1H), 7.29 (dd, J = 7.6, 1.6 Hz, 1H), 7.18 – 7.11 (m, 6H), 6.94 (s, 1H), 3.03 (d, J = 22.5 Hz, 1H), 2.83-2.73 (m, 2H), 2.76 (d, J = 22.5 Hz, 1H), 2.44-2.38 (m, 1H), 2.21-2.15 (m, 1H), 2.05 (s, 3H), 1.75-1.57 (m, 3H), 1.55-1.48 (m, 1H). ¹³C NMR (126 MHz, CDCl3): δ 145.39, 142.70, 141.34, 140.67, 139.91, 138.59, 136.35, 135.25, 130.48, 130.44, 130.16, 128.65, 127.68, 127.44, 127.23, 126.77, 126.57, 119.54, 42.45, 30.21, 27.78, 23.39, 23.14, 16.78. [0209] (9-(3,5-Di-tert-butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro- cyclopenta[b]naphthalenyl)lithium nBuLi (6.72 mL, 1.6 M in hexane, 10.7 mmol) was added dropwise to a precooled solution (-30°C) of 9-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-1H- cyclopenta[b]naphthalene (4.12 g, 10.2 mmol) in Et₂O (50 mL). The resulting mixture was gradually warmed to the ambient temperature. The reaction volume was then reduced to ca 1/3 of the initial volume upon evaporation of volatiles and the obtained precipitate was collected by filtration and washed with n-hexane (3 ^ 50 mL). Drying in vacuo gave a white crystalline product. Yield: 3.45 g, 83%. ¹H NMR (400 MHz, THF-d₈): δ 7.36 (s, 2H), 6.97 (s, 1H), 5.67 (s, 1H), 5.45 (s, 1H), 3.77 (s, 3H), 2.87 (t, J = 6.5 Hz, 2H), 2.67 (t, J = 6.3 Hz, 2H), 2.30 (s, 3H), 1.80-1.73 (m, 2H), 1.70-1.64 (m, 2H), 1.50 (s, 18H). ¹³C NMR (101 MHz, THF-d8): δ 157.44, 141.95, 138.69, 130.29, 129.39, 128.59, 128.57, 126.84, 123.34, 120.04, 117.61, 92.32, 90.98, 64.33, 36.17, 32.63, 32.45, 31.82, 28.98, 25.78, 16.39. [0210] (9- butyl)phenyl)-2-methyl-5,6,7,8-tetrahydro- cyclopenta[b]naphthalenyl)lithium nBuLi (1.30 mL, 2.70 M in hexane, 3.51 mmol) was added dropwise to a precooled solution (-40°C) of 9-(4-(tert-butyl)phenyl)-2-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene (1.10 g, 3.48 mmol) in Et₂O (15 mL). The resulting mixture was gradually warmed to the ambient temperature and the volatiles were evaporated. The resulting product was washed with n-pentane (2 ^ 5 mL) and dried in vacuo. The product was isolated as an adduct with 0.5 equiv. of Et2O. Yield: 1.12 g, 88%. ¹H NMR (400 MHz, THF-d8): δ 7.34 (d, J = 7.9 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 7.02 (s, 1H), 5.75 (s, 1H), 5.70 (s, 1H), 3.43 (q, J = 7.0 Hz, 2H, OCH₂CH₃), 2.96 (t, J = 6.6 Hz, 2H), 2.67 (t, J = 6.2 Hz, 2H), 2.38 (s, 3H), 2.00 – 1.82 (m, 2H), 1.82 – 1.67 (m, 2H), 1.39 (s, 9H), 1.16 (t, J = 7.0 Hz, 3H, OCH2CH3). ¹³C NMR (101 MHz, THF-d8): δ 146.39, 143.48, 129.33, 128.50, 127.66, 125.99, 125.56, 123.73, 123.63, 118.30, 118.17, 92.62, 89.53, 65.35, 33.94, 30.99, 29.19, 27.53, 25.05, 24.87, 15.62, 14.73. [0211] 9- 1'-biphenyl]-2-yl)-2-methyl-5,6,7,8-tetrahydro- cyclopenta[b]naphthalenyl)lithium nBuLi (0.78 mL, 2.50 M in hexane, 1.95 mmol) was added dropwise to a precooled solution (-40°C) of 9-([1,1'-biphenyl]-2-yl)-2-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene (0.65 g, 1.93 mmol) in Et₂O (10 mL). The resulting mixture was gradually warmed to the ambient temperature and the obtained precipitate was collected by filtration, washed with n-pentane (2 ^ 5 mL) and dried in vacuo. Yield: 0.60 g, 85%. ¹H NMR (400 MHz, THF-d₈) δ 7.50 – 7.41 (m, 1H), 7.39 – 7.25 (m, 3H), 7.23 – 7.14 (m, 2H), 7.03 – 6.94 (m, 3H), 6.90 (s, 1H), 5.65 (s, 1H), 5.34 (s, 1H), 2.75-2.61 (m, 2H), 2.30 (s, 3H), 2.24 – 2.09 (m, 1H), 2.04-1.96 (m, 1H), 1.63-1.54 (m, 1H), 1.48 – 1.34 (m, 2H), 1.27 – 1.20 (m, 1H). ¹³C NMR (101 MHz, THF-d8): δ 142.51, 142.29, 141.55, 131.63, 129.11, 128.87, 128.35, 128.21, 127.10, 126.81, 125.99, 125.97, 125.58, 125.41, 122.32, 119.73, 117.06, 91.72, 90.39, 30.88, 27.16, 24.25, 24.16, 15.56. [0212] (4-(3,5-Di-tert-butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-1H- cyclopenta[b]naphthalen-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane A suspension of (9-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro- cyclopenta[b]naphthalenyl)lithium (3.45 g, 8.44 mmol) in diethyl ether (5 mL) was added to a stirring solution of dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate (2.75 g, 8.36 mmol) in diethyl ether (20 mL) at -35°C. The reaction was allowed to warm up to ambient temperature and stirred for 1 hour. Then, the volatiles were removed and the residue was dried under vacuum. The product was extracted into n-pentane (2 x 20mL) and filtered through a short celite plug. Concentration under a stream of nitrogen and drying in vacuo afforded the product as a white foam. Yield: 4.84 g (99%). ¹H NMR (400 MHz, C₆D₆): δ 7.56 (s, 1H), 7.54 (s, 1H), 7.39 (s, 1H), 6.66 (s, 1H), 3.73 (s, 1H), 3.61 (s, 3H), 3.32 (s, 1H), 3.02-2.92 (m, 2H), 2.91-2.82 (m, 2H), 2.07 (s, 6H), 2.00 (s, 3H), 1.91 (s, 6H), 1.86-1.65 (m, 4H), 1.60 (s, 9H), 1.59 (s, 9H), -0.05 (s, 3H), -0.11 (s, 3H). ¹³C NMR (101 MHz, CDCl3): δ 158.13, 145.60, 142.95, 142.91, 136.36, 136.29, 135.23, 134.21, 132.84, 131.86, 131.41, 128.76, 128.53, 126.79, 123.27, 63.86, 47.18, 35.77, 35.75, 32.27, 32.24, 30.79, 28.52, 23.92, 23.51, 22.44, 17.83, 14.82, 14.73, 14.14, 11.17, -5.41, -5.66. [0213] (4-(4-(tert-Butyl)phenyl)-2-methyl-5,6,7,8-tetrahydro-1H- A solution of (9-(4-(tert-butyl)phenyl)-2-methyl-5,6,7,8-tetrahydro- cyclopenta[b]naphthalenyl)lithium (adduct with 0.5 equiv. of Et₂O, 0.542 g, 1.48 mmol) in diethyl ether (5 mL) was added to a stirring solution of dimethyl(2,3,4,5- tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate (0.480 g, 1.46 mmol) in diethyl ether (20 mL) at -30°C. The reaction was allowed to warm up to ambient temperature and stirred for 90 minutes. Then, the volatiles were removed and the residue was dried under vacuum. The product was extracted into n-pentane (2 x 20mL) and filtered through a short celite plug. Concentration under a stream of nitrogen and drying in vacuo afforded the product as a white crystalline solid. Yield: 0.656 g (90%). ¹H NMR (400 MHz, CDCl₃): δ 7.41 (d, J = 8.3 Hz, 2H), 7.27 (d, J = 8.3 Hz, 2H), 7.17 (s, 1H), 6.69 (s, 1H), 3.64 (s, 1H), 3.27 (s, 1H), 3.07–2.85 (m, 2H), 2.79–2.58 (m, 2H), 2.29 (s, 3H), 2.04 (s, 3H), 1.99 (s, 3H), 1.92-1.87 (m, 2H), 1.84 (s, 6H), 1.78-1.73 (m, 2H), 1.40 (s, 9H), -0.20 (s, 3H), -0.25 (s, 3H).¹³C NMR (101 MHz, CDCl₃): δ 148.84, 147.28, 143.14, 141.86, 140.22, 136.77, 136.56, 133.02, 131.13, 129.19, 128.07, 124.69, 124.20, 122.48, 47.46, 34.48, 31.47, 28.68, 27.02, 23.63, 23.08, 18.12, 14.88, 14.80, 11.23, 11.19, -5.21, -5.42. [0214] (4 iphenyl]-2-yl)-2-methyl-5,6,7,8-tetrahydro-1H- cyclopenta[b]naphthalen-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane A solution of 9-([1,1'-biphenyl]-2-yl)-2-methyl-5,6,7,8-tetrahydro- cyclopenta[b]naphthalenyl)lithium (587 mg, 1.65 mmol) in diethyl ether (5 mL) was added to a stirring solution of dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate (535 mg, 1.63 mmol) in diethyl ether (10 mL) at -35°C. The reaction was allowed to warm up to ambient temperature and stirred for 2 hours. Then, the volatiles were removed and the residue was dried under vacuum. The product was extracted into n-pentane (2 x 10 mL) and filtered through a short celite plug. Concentration under a stream of nitrogen and drying in vacuo afforded a white foam consisting of two isomers of the product (ca 1:1.6). Yield: 0.84 g (99%). ¹H NMR (400 MHz, CDCl3): δ 7.57-7.46 (m, 6H), 7.34-7.28 (m, 3H), 7.26–7.02 (m, 7H), 6.28 (s, 0.6H), 6.24 (s, 1H), 3.69 (s, 0.6H), 3.63 (s, 1H), 3.35 (s, 1.6H), 2.96 – 2.44 (m, 6H), 2.27-2.08 (m, 18H), 1.96-1.90 (m, 10H), -0.17 (s, 1.6H), -0.23 (s, 1.6H), -0.30 (s, 3H), -0.38 (s, 3H). ¹³C NMR (101 MHz, CDCl3): δ 146.30, 145.89, 142.94, 142.64, 142.05, 141.97, 141.72, 141.68, 141.65, 141.39, 139.07, 138.77, 136.66, 136.52, 133.15, 133.12, 132.50, 132.30, 131.62, 131.54, 131.51, 131.13, 131.04, 130.04, 129.85, 129.12, 129.02, 127.61, 127.58, 127.22, 127.04, 126.40, 126.33, 126.19, 126.02, 123.11, 122.91, 47.11, 46.72, 30.44, 30.38, 27.76, 27.44, 23.49, 23.33, 23.26, 18.08, 14.99, 14.94, 11.34, 11.32, -5.44, -5.72, -5.92, -6.16. [0215] Catalyst I1 nBuLi (0.83 mL, 2.5 M in hexane, 2.07 mmol) was added dropwise to a precooled solution (-30°C) of (4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-1H- cyclopenta[b]naphthalen-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (588 mg, 1.01 mmol) in Et₂O (15 mL). The mixture was allowed to warm up to the ambient temperature under stirring over 1 hour. The resulting bright yellow suspension was cooled back to -30°C before solid ZrCl4 (238 mg, 1.02 mmol) was added in small portions over 10 minutes. The mixture was stirred for 10 minutes at -30°C and then the reaction mixture was gradually warmed up to the ambient temperature. Additional stirring for 1 hour gave a yellow precipitate. Volatiles were then evaporated, and the product was extracted into CH2Cl2 (15 mL). Filtration through a celite plug and evaporation of the solvent gave an orange oil which was suspended in n-hexane and stirred for 30 minutes. The mixture was filtered from insoluble residues and the filtration cake was washed with n-hexane (10 mL). Concentration to 5 mL and cooling to -35°C for the combined hexane fraction gave 222 mg of the precipitated yellow-orange product after drying. n-Hexane was evaporated from the mother liquor and n-pentane was added (5 mL) to afford additional 160 mg of the product over 16 hours at -35°C. Yield: 382 mg (51%). ¹H NMR (400 MHz, CDCl3) δ 7.67 (d, JHH = 2.21 Hz, 1H), 7.25 (br s, 1H), 7.03 (d, JHH = 2.21 Hz, 1H), 6.52 (s, 1H), 3.76 (s, 3H, OCH₃), 2.83-2.71 (m, 4H), 2.22 (s, 3H), 2.04 (s, 3H), 1.99 (s, 3H), 1.94 (s, 3H), 1.93 (s, 3H), 1.79-1.73 (m, 4H), 1.47 (s, 9H, tBu), 1.43 (s, 9H, tBu), 1.20 (s, 3H), 1.07 (s, 3H).¹³C NMR (101 MHz, CDCl3) δ 158.23, 143.46, 142.48, 137.29, 136.85, 135.68, 135.45, 135.19, 134.39, 133.87, 132.94, 128.35, 127.60, 127.15, 126.78, 123.75, 122.29, 120.54, 93.68, 80.94, 64.12, 36.16, 35.76, 32.41, 32.24, 30.90, 27.64, 23.21, 22.47, 18.13, 15.81, 15.49, 12.55, 12.18, 3.21, 3.18. [0216] Catalyst I2 nBuLi (1.00 mL, 2.5 M in hexane, 2.50 mmol) was added dropwise to a precooled solution (-30°C) of [4-(4-tert-butylphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalen-1- yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (588 mg, 1.19 mmol) in Et₂O (10 mL). The reaction mixture was warmed up to the ambient temperature under stirring. Then, the solvent was evaporated, and the formed yellowish oil was washed several times with n-pentane (10 mL totally) to give a solid product. This intermediate product was dried in vacuo and used for the next step. The dilithium salt was dissolved in the mixture of Et₂O (10 mL) and THF (0.1 mL). The resulting solution was cooled to -30°C before solid ZrCl4 (280 mg, 1.20 mmol) was added in small portions. The obtained mixture was stirred for 10 minutes at -30°C and then the temperature was increased to ambient over 1 hour. The bright yellow suspension was stirred for additional 1 hour. The solvent was evaporated, and the product was extracted into dichloromethane (10 mL). The resulting suspension was filtered through a celite plug followed by evaporation of the solvent. The obtained product was washed with n-pentane (5 mL) and dried in vacuo. Yield: 428 mg of yellow solid (55%). ¹H NMR (400 MHz, CDCl3): δ 7.72 (d, JHH = 8.20 Hz, 1H), 7.50 (d, JHH = 8.20 Hz, 1H), 7.43 (d, JHH = 7.75 Hz, 1H), 7.29 (s, 1H), 7.14 (d, J_HH = 7.75 Hz, 1H), 6.58 (s, 1H), 2.81-2.67 (m, 4H), 2.23 (s, 3H), 2.07 (s, 3H), 2.01 (s, 3H), 1.97 (s, 3H), 1.96 (s, 3H), 1.78-1.68 (m, 4H), 1.40 (s, 9H), 1.23 (s, 3H), 1.10 (s, 3H).¹³C NMR (101 MHz, CDCl3): δ 149.68, 137.45, 136.83, 135.86, 135.85, 135.05, 134.83, 134.51, 133.88, 129.09, 129.01, 127.40, 126.83, 125.51, 124.66, 123.82, 122.59, 120.62, 93.61, 80.80, 34.60, 31.47, 30.92, 27.57, 23.13, 22.50, 18.04, 15.80, 15.48, 12.57, 12.15, 3.21, 3.18. [0217] Catalyst I3 nBuLi (1.34 mL, 2.5 M in hexane, 3.34 mmol) was added to a precooled solution (-30°C) of the mixture of two isomers of 4-([1,1'-biphenyl]-2-yl)-2-methyl-5,6,7,8-tetrahydro-1H- cyclopenta[b]naphthalen-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (840 mg, 1.63 mmol) in Et₂O (15 mL). The mixture was allowed to warm up to the ambient temperature and stirred for additional 1 hour. Evaporation of Et2O gave an oily product which was triturated with n-pentane and dried in vacuo to give an orange-red solid. This intermediate product was dissolved in Et₂O (10 mL) and cooled to -30°C. Solid ZrCl₄ (384 mg, 1.65 mmol) was added to the resulting mixture. The mixture was stirred for 10 minutes and then the temperature was increased to ambient. The mixture was stirred for 3 days to give a yellow mixture. The solvent was evaporated, and the obtained oily product extracted into dichloromethane (10 mL). The filtrate was evaporated and the product was extracted from the resulting crude oil by n-pentane (20 mL). n-Pentane was evaporated to give a solid which was rinsed with small amount of n-pentane (1 mL) and dried in vacuo to give a bright yellow product having only one isomer. Yield: 200 mg (18%). ¹H NMR (400 MHz, CDCl₃): δ 7.92-7.89 (m, 1H), 7.45-7.44 (m, 4H), 7.14 (s, 1H), 7.07-7.05 (m, 4H), 6.94-6.92 (m, 2H), 6.49 (s, 1H), 2.59- 2.46 (m, 2H), 2.20 (s, 3H), 2.03 (s, 3H), 1.98 (s, 3H), 1.93 (s, 3H), 1.91 (s, 3H), 1.60-1.41 (m, 2H), 1.30-1.27 (m, 2H), 1.18 (s, 3H), 1.08 (s, 3H). ¹³C NMR (101 MHz, CDCl₃): δ 141.47, 141.19, 137.44, 137.07, 136.72, 136.36, 135.46, 134.67, 133.55, 133.17, 130.30, 129.73, 128.88, 127.70, 127.62, 127.50, 127.44, 126.44, 126.31, 123.58, 122.55, 121.06, 93.53, 80.45, 30.65, 27.11, 22.40, 22.36, 17.97, 15.71, 15.46, 12.58, 12.18, 3.20, 3.14. Syntheses of Catalysts I4 and I5 [0218] 1,2,3,4-Tetrahydro-1,4-ethanonaphthalene The solution of 1,4-dihydro-1,4-ethanonaphthalene (3.25 g, 20.8 mmol, prepared according to Y. Ishii et al., Tetrahedron 2015, 71, 8892) in methanol (50 mL) was slowly added to a 100 mL flask containing Pd/C (511 mg, 10 wt% Pt) under H₂ atmosphere (1 atm). The reaction was stirred under constant hydrogen flow at 25°C for 16 hours. Then, the reaction mixture was sparged with N₂ for 30 minutes before filtration through a short celite plug. The evaporation of solvent gave colorless crystals of the product. Yield: 3.12 g (95%). ¹H NMR (400 MHz, CDCl3): δ 7.28–7.17 (m, 4H), 3.05 (m, 2H), 1.90–1.76 (m, 4H), 1.52–1.38 (m, 4H). [0219] 2-Methyl-2,3,5,6,7,8-hexahydro-1 1-one A solution containing 1,2,3,4-tetrahydro-1,4-ethanonaphthalene (3.12 g, 19.7 mmol) and 2-bromo-2-methyl-propanoyl bromide (4.53 g, 19.7 mmol) in dichloromethane (50 mL) was added over 30 minutes to the stirred suspension of AlCl3 (6.57 g, 49.3 mmol) in dichloromethane (100 mL) at 0°C. After the addition was completed, the reaction mixture was allowed to warm to the ambient temperature and stirred for 16 hours. Then, the reaction mixture was transferred to a separatory funnel containing ice. The organic layer was separated, and the residual aqueous layer was extracted with CH₂Cl₂ (2 ^ 50 mL). The combined organic phase was subsequently washed with 1M hydrochloric acid (50 mL), water (100 mL), aqueous NaHCO3 (100 mL), and brine (2 ^ 100 mL) before drying over MgSO4. The evaporation of solvent gave an oily residue which was dissolved in the mixture of n-hexane and dichloromethane (2:1, v:v, respectively) and passed through a short silica plug. After evaporation, the product was further purified by refluxing in n-hexane (5 mL) for a few minutes and washing the resulting white precipitate with cold n-hexane (5 mL). The product was dried under vacuum. Yield: 3.34 g (75%). ¹H NMR (500 MHz, CDCl3): δ 7.52 (s, 1H), 7.22 (s, 1H), 3.41–3.33 (m, 1H), 3.06 (m, 2H), 2.75–2.64 (m, 2H), 1.88–1.77 (m, 4H), 1.40 (m, 4H), 1.31 (d, J = 7.5 Hz, 3H).¹³C NMR (126 MHz, CDCl₃): δ 209.54, 152.75, 152.23, 143.92, 134.45, 121.60, 118.49, 42.01, 34.97, 34.95, 34.10, 26.03, 26.00, 25.86, 25.84, 16.43. [0220] 4-Bromo-2-methyl-2,3,5,6,7,8-hexahydro-1 5,8-ethanocyclopenta[b]naphthalen- 1-one. Under the nitrogen atmosphere, a cold solution (0°C) of 2-methyl-2,3,5,6,7,8-hexahydro-1H- 5,8-ethanocyclopenta[b]naphthalen-1-one (3.33 g, 14.7 mmol) in CH₂Cl₂ (50 mL) was slowly added under stirring to the solution of AlBr₃ (10.9 g, 40.8 mmol) in CH₂Cl₂ (50 mL) at 0°C. The resulting mixture was stirred for 1 hour at 0°C before the solution of Br2 (2.47 g, 15.4 mmol) in CH₂Cl₂ (25 mL) was added in the absence of ambient light over 45 minutes at 0°C. The temperature of the reaction mixture was gradually increased to 25°C and the mixture was stirred for 14 hours. Then, the obtained mixture was poured into ice water (100 mL), and the formed organic layer was separated. The aqueous layer was extracted with CH₂Cl₂ (2 ^ 75 mL) and the combined organic layer was subsequently washed with aqueous Na2CO3 (100 mL), water (2 ^ 100 mL), and brine (2 ^ 100 mL). The combined organic layer was then dried over MgSO₄, filtered and evaporated to give an orange oil. The product was dissolved in the CH₂Cl₂/n-hexane mixture (1:2, v:v, respectively) and passed through a short silica gel plug. The solvent was evaporated and the product was further purified on Biotage automated column using the mixture of ethyl acetate and n-hexane (1:9; v:v, respectively) as an eluent and silica gel to give the desired product as a light orange oil. Yield: 3.18 g (71%). ¹H NMR (400 MHz, CDCl3): δ 7.49 (s, 1H), 3.62 (m, 1H), 3.41–3.32 (m, 1H), 3.11 (m, 1H), 2.78–2.63 (m, 2H), 1.90–1.75 (m, 4H), 1.44-1.36 (m, 4H), 1.33 (d, J = 7.3 Hz, 3H).¹³C NMR (101 MHz, CDCl₃): δ 209.01, 151.68, 150.78, 146.04, 135.94, 119.04, 117.67, 42.00, 36.53, 34.87, 33.39, 25.64, 25.58, 24.96, 24.93, 16.35. [0221] 9-Bromo-2-methyl-5,6,7,8-tetrahydro-1H-5,8-ethanocyclopenta[b]naphthalene Solid sodium borohydride (1.18 g, 31.3 mmol) was added to a pre-cooled, stirring suspension of 4-bromo-2-methyl-2,3,5,6,7,8-hexahydro-1H-5,8-ethanocyclopenta[b]naphthalen-1-one (3.18 g, 10.4 mmol) in methanol (50 mL) at 0°C. The reaction mixture was then stirred at room temperature for 2 hours before being concentrated to ca 20 mL. Then, aqueous hydrochloric acid (1M, 50 mL) and diethyl ether (50 mL) were added. The obtained aqueous layer was separated and extracted with Et₂O/EtOAc (1:1, 3 ^ 20 mL). The combined organic phase was subsequently washed with aqueous hydrochloric acid (1M, 50 mL), water (3 ^ 50 mL), and brine (2 ^ 50 mL), and finally dried over anhydrous MgSO₄. Evaporation of the solvent afforded a white solid product which was used for the next step without any purification. This intermediate product and catalytic amount of p-toluenesulfonic acid monohydrate (40 mg, 0.207 mmol) were dissolved in toluene (75 mL) and the obtained mixture was refluxed for 90 minutes. Then, toluene was evaporated to ca 10 mL of the reaction volume the mixture was transferred into a separatory funnel with water (50 mL). The aqueous layer was extracted with (3 ^ 25 mL) and the combined organic phase was subsequently washed with water (2 ^ 50 mL), aqueous Na2CO3 (2 ^ 50 mL), and brine (2 ^ 50 mL), and finally dried over anhydrous MgSO4. Evaporation of solvent gave a crude product which was purified by passing through a short silica plug using n-hexane/CH2Cl2 (3:1, v:v) as an eluent. The product was isolated as a light yellow solid after evaporation of solvents. Overall yield over two steps: 2.97 g, 89%. ¹H NMR (500 MHz, CDCl3): δ 7.04 (s, 1H), 6.53 (s, 1H), 3.55 (m, 1H), 3.32 (s, 2H), 3.06 (m, 1H), 2.20 (s, 3H), 1.92–1.69 (m, 4H), 1.50–1.26 (m, 4H).¹³C NMR (126 MHz, CDCl3): δ 145.59, 144.69, 144.42, 140.79, 138.08, 127.12, 116.20, 114.77, 44.67, 35.11, 32.47, 26.10, 25.78, 16.72. [0222] 9-(3,5-di-tert-Butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-5,8- ethanocyclopenta[b]naphthalene 9-Bromo-2-methyl-5,6,7,8-tetrahydro-1H-5,8-ethanocyclopenta[b]naphthalene (0.47 g, 1.63 mmol), (3,5-di-tert-butyl-4-methoxyphenyl)boronic acid (0.42 g, 1.71 mmol), K₂CO₃ (0.49 g, 3.58 mmol), bis(dibenzylideneacetone)palladium(0) (46.7 mg, 0.0813 mmol), 1,3,5,7- tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (71.3 mg, 0.244 mmol) and THF (25 mL) were added to a pressure-resistant flask followed by degassed water (4 mL). The flask was sealed and heated with vigorous stirring at 80°C for 60 hours. Then, the flask was cooled to the ambient temperature and the reaction volume was reduced to ca 5 mL. The product was extracted into Et₂O/EtOAc (1:1, 3 ^ 25 mL) and the combined organic phase was subsequently washed with water (3 ^ 50 mL), saturated sodium carbonate solution (2 ^ 50 mL) and brine (2 ^ 50 mL). The obtained organic phase was dried over MgSO₄ and evaporated to give an orange oil. The product was dissolved in the CH2Cl2/n-hexane mixture (1:4, v:v, respectively) and passed through a short silica gel plug. The solvent was evaporated and the product was further purified on Biotage automated column using silica gel and the mixture of ethyl acetate and n-hexane (8:92, v:v, respectively) as an eluent. Yield: 0.34 g (49%). ¹H NMR (400 MHz, CDCl₃): δ 7.31 (s, 2H), 7.16 (s, 1H), 6.59 (m, 1H), 3.85 (s, 3H), 3.26 (s, 2H), 3.18 (m, 1H), 3.14 (m, 1H), 2.18 (s, 3H), 1.92–1.75 (m, 4H), 1.55 (s, 18H), 1.53 – 1.48 (m, 4H).¹³C NMR (126 MHz, CDCl3): δ 157.97, 145.33, 143.35, 143.10, 142.81, 139.44, 137.31, 134.10, 133.41, 127.81, 127.17, 114.74, 64.12, 42.90, 35.84, 35.05, 32.30, 30.16, 26.54, 26.44, 16.79. [0223] 9-(4-(tert-Butyl)phenyl)-2-methyl-5,6,7,8-tetrahydro-1H-5,8- ethanocyclopenta[b]naphthalene 9-Bromo-2-methyl-5,6,7,8-tetrahydro-1H-5,8-ethanocyclopenta[b]naphthalene (0.50 g, 1.73 mmol), (4-tert-butylphenyl)boronic acid (0.34 g, 1.90 mmol), K₂CO₃ (0.53 g, 3.80 mmol), bis(dibenzylideneacetone)palladium(0) (49.7 mg, 0.0864 mmol), 1,3,5,7-tetramethyl-6- phenyl-2,4,8-trioxa-6-phosphaadamantane (75.8 mg, 0.259 mmol) and THF (25 mL) were added to a pressure-resistant flask followed by degassed water (4 mL). The flask was sealed and heated with vigorous stirring at 80°C for 24 hours. Then, the flask was cooled to the ambient temperature and the reaction volume was reduced to ca 5 mL. Water (20 mL) was added, and the product was extracted into Et₂O/EtOAc (1:1, 3 ^ 25 mL). The combined organic phase was subsequently washed with water (3 ^ 50 mL), saturated sodium carbonate solution (2 ^ 50 mL) and brine (2 ^ 50 mL). The obtained organic phase was dried over MgSO₄ and evaporated to give a red-orange oil. The product was dissolved in the CH2Cl2/n-hexane mixture (1:4, v:v, respectively) and passed through a short silica gel plug. The solvent was evaporated and the product was further purified on Biotage automated column using silica gel and the mixture of ethyl acetate and n-hexane (6:94, v:v, respectively) as an eluent. The obtained white solid product was recrystallized from boiling n-pentane (10 mL), additionally washed with isohexane (5 mL) and dried in vacuo. Yield: 0.38 g (64%). ¹H NMR (500 MHz, CDCl3): δ 7.47 (d, J = 8.4 Hz, 2H), 7.28 (d, J = 8.4 Hz, 2H), 7.11 (s, 1H), 6.53 (s, 1H), 3.18 (s, 2H), 3.08 (m, 2H), 2.11 (s, 3H), 1.83-1.77 (m, 2H), 1.76–1.67 (m, 2H), 1.53–1.31 (m, 4H), 1.43 (s, 9H). ¹³C NMR (126 MHz, CDCl₃): δ 149.31, 145.37, 143.14, 142.96, 139.60, 137.38, 136.50, 133.35, 128.95, 127.06, 124.96, 114.84, 42.75, 35.01, 34.57, 31.48, 30.00, 26.53, 26.43, 16.75. [0224] (9-(3,5-di-tert-Butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-5,8- ethanocyclopenta[b]naphthalenyl)lithium nBuLi (0.53 mL, 1.60 M in hexane, 0.85 mmol) was added dropwise to a precooled solution (-35°C) of 9-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-5,8- ethanocyclopenta[b]naphthalene (0.33 g, 0.77 mmol) in Et₂O (30 mL). The resulting mixture was gradually warmed to the ambient temperature and the volatiles were evaporated. The resulting solid product was suspended in n-pentane (10 mL) and collected via filtration. The filtration cake was washed with n-pentane (3 ^ 5 mL) and dried in vacuo. Yield: 0.27 g, 81%. ¹H NMR (400 MHz, THF-d₈): δ 7.48 (s, 2H), 7.02 (s, 1H), 5.75 (d, J = 2.1 Hz, 1H), 5.67 (d, J = 2.1 Hz, 1H), 3.79 (s, 3H), 3.18 (m, 1H), 2.88 (m, 1H), 2.32 (s, 3H), 1.85–1.70 (m, 4H), 1.56- 1.45 (m, 4H), 1.52 (s, 18H).¹³C NMR (126 MHz, THF-d8): δ 157.64, 142.20, 137.90, 131.58, 129.69, 128.30, 127.64, 127.56, 127.14, 125.89, 113.18, 92.59, 92.39, 64.50, 36.47, 36.38, 32.86, 31.06, 28.84, 28.78, 16.59. [0225] (9-(4-(tert-Butyl)phenyl)-2-methyl-5,6,7,8-tetrahydro-5,8- ethanocyclopenta[b]naphthalenyl)-lithium nBuLi (0.76 mL, 1.60 M in hexane, 1.22 mmol) was added dropwise to a precooled solution (-35°C) of 9-(4-(tert-butyl)phenyl)-2-methyl-5,6,7,8-tetrahydro-1H-5,8- ethanocyclopenta[b]naphthalene (0.38 g, 1.11 mmol) in Et2O (30 mL). The resulting mixture was gradually warmed to the ambient temperature and the volatiles were evaporated. The resulting solid product was suspended in n-pentane (10 mL) and collected via filtration. The filtration cake was washed with n-pentane (3 ^ 5 mL) and dried in vacuo. Yield: 0.32 g, 82%. ¹H NMR (400 MHz, THF-d8): δ 7.48–7.37 (m, 4H), 7.04 (s, 1H), 5.78 (d, J = 2.1 Hz, 1H), 5.64 (d, J = 2.1 Hz, 1H), 3.13 (m, 1H), 2.88 (m, 1H), 2.33 (s, 3H), 1.88–1.56 (m, 4H), 1.56–1.23 (m, 4H), 1.42 (s, 9H).¹³C NMR (101 MHz, THF-d₈): δ 147.89, 141.02, 131.42, 130.84, 128.30, 127.78, 127.69, 126.48, 125.86, 124.83, 113.34, 92.39, 92.37, 36.42, 31.98, 31.81, 30.82, 28.82, 28.70, 16.53. [0226] (4-(3,5-di-tert-Butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-5,8- naphthalen-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1- yl)silane A solution of (4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-5,8- ethanocyclopenta[b]naphthalenyl)lithium (0.271 g, 0.62 mmol) in diethyl ether (10 mL) and THF (0.25 mL) was added dropwise to a stirring solution of dimethyl(2,3,4,5- tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate (0.203 g, 0.617 mmol) in diethyl ether (10 mL) at -35°C. The reaction was allowed to warm up to ambient temperature and stirred for 30 minutes. Then, the volatiles were removed, and the residue was dried under vacuum. The product was extracted into n-pentane (15 mL) and filtered through a short celite plug. Concentration under a stream of nitrogen and drying in vacuo afforded the product as an orange powder. Yield: 0.347 g (92%). ¹H NMR (400 MHz, CDCl₃): δ 7.26-7.23 (m, 2H), 7.21 (s, 1H), 7.22 (s, 1H), 6.53 (s, 1H), 3.81 (s, 3H), 3.63 (s, 1H), 3.27-3.23 (m, 2H), 3.03 (m, 1H), 2.22 (s, 3H), 2.04 (s, 3H), 2.01 (s, 3H), 1.89 (s, 3H), 1.87 (s, 3H), 1.83-1.69 (m, 8H), 1.50 (s, 18H), -0.14 (s, 3H), -0.21 (s, 3H). ¹³C NMR (101 MHz, CDCl₃): δ 157.80, 145.55, 142.47, 142.38, 141.62, 139.70, 138.09, 136.58, 136.47, 133.39, 130.12, 128.65, 126.33, 118.07, 64.13, 47.58, 35.80, 35.77, 35.16, 32.28, 30.11, 26.86, 26.70, 26.53, 26.34, 18.02, 14.86, 14.71, 11.28, -4.80, -5.21. [0227] (4-(4-(tert-Butyl)phenyl)-2-methyl-5,6,7,8-tetrahydro-1H-5,8- ethanocyclopenta[b]naphthalen-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1- yl)silane A solution of (4-(4-(tert-butyl)phenyl)-2-methyl-5,6,7,8-tetrahydro-5,8- ethanocyclopenta[b]naphthalenyl)lithium (0.317 g, 0.91 mmol) in diethyl ether (10 mL) and THF (0.25 mL) was added dropwise to a stirring solution of dimethyl(2,3,4,5- tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate (0.296 g, 0.901 mmol) in diethyl ether (10 mL) at -35°C. The reaction was allowed to warm up to ambient temperature and stirred for 30 minutes. Then, the volatiles were removed, and the residue was dried under vacuum. The product was extracted into n-pentane (15 mL) and filtered through a short celite plug. Concentration under a stream of nitrogen and drying in vacuo afforded the product as an orange solid. Yield: 0.441 g (93%). ¹H NMR (500 MHz, CDCl₃): δ 7.49-7.47 (m, 2H), 7.31- 7.29 (m, 2H), 7.22 (s, 1H), 6.48 (s, 1H), 3.65 (s, 1H), 3.27 (s, 1H), 3.18 (m, 1H), 3.03 (m, 1H), 2.20 (s, 3H), 2.03 (s, 3H), 2.01 (s, 3H), 1.89 (s, 3H), 1.88 (s, 3H), 1.87-1.68 (m, 8H), 1.43 (s, 9H), -0.17 (s, 3H), -0.24 (s, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 148.95, 145.51, 142.24, 141.74, 139.52, 138.18, 136.58, 136.54, 136.44, 129.97, 129.67, 129.59, 129.37, 126.26, 124.72, 118.20, 47.59, 35.14, 34.56, 31.51, 29.95, 26.87, 26.69, 26.53, 26.35, 17.89, 14.86, 14.69, 14.07, 11.28, 11.26, -4.93, -5.31. [0228] Catalyst I4 nBuLi (0.74 mL, 1.6 M in hexane, 1.18 mmol) was added to a precooled solution (-30°C) of (4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-5,8- ethanocyclopenta[b]naphthalen-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1- yl)silane (325 mg, 0.535 mmol) in Et₂O (5 mL). The mixture was allowed to warm up to the ambient temperature and stirred for additional 2 hours. Then, the mixture was cooled back to -30°C and solid ZrCl4 (126 mg, 0.54 mmol) was added. The mixture was stirred for 10 minutes and then the temperature was increased to ambient. The mixture was stirred for 2 hours to give a yellow mixture. The solvent was evaporated, and the obtained product was extracted into dichloromethane (10 mL) and filtered through a celite plug. The filtrate was evaporated, and the product was washed with n-pentane (20 mL) to give a bright yellow solid. Yield: 221 mg (54%). ¹H NMR (400 MHz, CDCl₃) δ 7.77 (d, J = 2.2 Hz, 1H), 7.30 (s, 1H), 7.12 (d, J = 2.2 Hz, 1H), 6.76 (s, 1H), 3.80 (s, 3H), 3.23 (m, 1H), 2.88 (m, 1H), 2.27 (s, 3H), 2.09 (s, 3H), 2.03 (s, 3H), 1.97 (s, 3H), 1.94 (s, 3H), 1.87 (m, 2H), 1.82–1.59 (m, 6H), 1.52 (s, 9H), 1.48 (s, 9H), 1.25 (s, 3H), 1.11 (s, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 158.30, 143.49, 143.46, 142.41, 141.92, 137.32, 134.43, 133.54, 131.99, 131.84, 128.81, 128.04, 126.89, 124.04, 120.88, 117.51, 93.67, 81.73, 64.11, 36.18, 35.71, 35.56, 32.44, 32.18, 30.27, 27.47, 26.24, 25.94, 25.78, 18.14, 15.89, 15.50, 12.57, 12.20, 3.26. [0229] Catalyst I5. nBuLi (1.11 mL, 1.6 M in hexane, 1.78 mmol) was added to a precooled solution (-35°C) of (4-(4-(tert-butyl)phenyl)-2-methyl-5,6,7,8-tetrahydro-1H-5,8-ethanocyclopenta [b]naphthalene-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (441 mg, 0.847 mmol) in Et2O (6 mL). The mixture was allowed to warm up to the ambient temperature and stirred for additional 1 hour. Then, the mixture was cooled back to -35°C and solid ZrCl4 (199 mg, 0.855 mmol) was added. The mixture was stirred for 5 minutes and then the temperature was elevated to the ambient temperature. The mixture was stirred for 1 hour to give a yellow mixture. The solvent was then evaporated and the obtained product was washed by n-pentane (5 mL). Extraction into toluene (5 mL) and filtration through a celite plug afforded an orange-yellow solid after evaporation. Yield: 150 mg (26%). ¹H NMR (400 MHz, CDCl₃) δ 7.78 (d, J = 7.3 Hz, 1H), 7.54 (d, J = 7.3 Hz, 1H), 7.46 (d, J = 7.3 Hz, 1H), 7.32 (s, 1H), 7.29 (d, J = 7.3 Hz, 1H), 6.78 (s, 1H), 3.20 (s, 1H), 2.89 (m, 1H), 2.27 (s, 3H), 2.09 (s, 3H), 2.03 (s, 3H), 1.97 (s, 3H), 1.94 (s, 3H), 1.84-1.56 (m, 8H); 1.42 (s, 9H), 1.26 (s, 3H), 1.12 (s, 3H). ¹³C NMR (101 MHz, CDCl3) δ 149.73, 143.50, 142.24, 137.49, 134.97, 134.60, 134.41, 133.47, 131.22, 129.50, 129.32, 127.16, 126.88, 125.56, 124.66, 124.03, 121.09, 117.77, 93.59, 81.53, 35.54, 34.63, 31.48, 30.02, 27.35, 26.17, 26.03, 25.81, 18.03, 15.88, 15.50, 12.60, 12.18, 3.27, 3.25. Synthesis of Catalyst I6 [0230] 2-Methyl-2,3,5,6,7,8-hexahydro-1H-5,8-methanocyclopenta[b]naphthalen-1-one A solution containing 1,2,3,4-tetrahydro-1,4-methanonaphthalene (3.71 g, 25.7 mmol, prepared according to the literature, J. Am. Chem. Soc. 2015, 137, 3454) and 2-bromo-2- methyl-propanoyl bromide (5.91 g, 25.7 mmol) in dichloromethane (75 mL) was added over 30 minutes to the stirred suspension of AlCl3 (8.58 g, 64.3 mmol) in dichloromethane (150 mL) at 0°C. After the addition was completed, the reaction mixture was allowed to warm to the ambient temperature and stirred for 16 hours. Then, the reaction mixture was transferred to a separatory funnel containing ice and 1 M HCl (75 mL). The organic layer was separated, and the residual aqueous layer was extracted with CH₂Cl₂ (2 ^ 50 mL). The combined organic phase was subsequently washed with 1M hydrochloric acid (50 mL), water (100 mL), aqueous NaHCO3 (100 mL), and brine (2 ^ 100 mL) before drying over MgSO4. The evaporation of solvent gave an oily residue which was dissolved in the mixture of n-hexane and dichloromethane (3:1, v:v, respectively) and passed through a short silica plug. After evaporation, the product was further purified on Biotage automated column using silica gel and the mixture of ethyl acetate and n-hexane (5:95, v:v, respectively) as an eluent. Yield: 4.45 g of an orange oil (75%). ¹H NMR (400 MHz, CDCl3): δ 7.46 (s, 1H), 7.18 (s, 1H), 3.36 (s, 2H), 3.35–3.20 (m, 1H), 2.70–2.57 (m, 2H), 1.98–1.84 (m, 2H), 1.73 (m, 1H), 1.55 (dt, J = 9.0, 1.4 Hz, 1H), 1.26 (dd, J = 7.3, 1.2 Hz, 3H), 1.20-1.13 (m, 2H). ¹³C NMR (126 MHz, CDCl₃): δ 209.06, 209.04, 156.92, 156.91, 153.07, 153.03, 148.07, 148.00, 134.44, 134.36, 118.40, 118.38, 115.26, 115.22, 48.83, 48.80, 43.98, 43.08, 42.10, 42.06, 35.02, 26.88, 26.85, 26.66, 26.63, 16.45, 16.40. [0231] 4-Bromo-2-methyl-2,3,5,6,7,8-hexahydro-1H-5,8- methanocyclopenta[b]naphthalen-1-one. Under the nitrogen atmosphere, a cold solution (0°C) of 2-methyl-2,3,5,6,7,8-hexahydro-1H- 5,8-methanocyclopenta[b]naphthalen-1-one (3.45 g, 16.3 mmol) in CH2Cl2 (50 mL) was slowly added under stirring to the solution of AlBr₃ (12.0 g, 45 mmol) in CH₂Cl₂ (75 mL) at 0°C. The resulting mixture was stirred for 1 hour at 0°C before the solution of Br₂ (2.65 g, 16.6 mmol) in CH2Cl2 (25 mL) was added in the absence of ambient light over 45 minutes at 0°C. The temperature of the reaction mixture was gradually increased to 25°C and the mixture was stirred for 16 hours. Then, the obtained mixture was poured into ice water (100 mL), and the formed organic layer was separated. The aqueous layer was extracted with CH2Cl2 (2 ^ 75 mL) and the combined organic layer was subsequently washed with aqueous Na₂CO₃ (100 mL), water (2 ^ 100 mL), and brine (2 ^ 100 mL). The combined organic layer was then dried over MgSO4, filtered and evaporated to give an orange oil. The product was dissolved in the CH₂Cl₂/n-hexane mixture (1:2, v:v, respectively) and passed through a short silica gel plug. The solvent was evaporated and the product was further purified on Biotage automated column using the mixture of ethyl acetate and n-hexane (9:91; v:v, respectively) as an eluent and silica gel to give the desired product as a white solid. Yield: 3.56 g (75%). ¹H NMR (400 MHz, CDCl₃): δ 7.42 (s, 1H), 3.62 (s, 1H), 3.48 (s, 1H), 3.26 (dt, J = 17.5, 8.0 Hz, 1H), 2.68 (ddp, J = 11.1, 7.4, 3.8 Hz, 1H), 2.57 (ddd, J = 17.5, 8.9, 3.8 Hz, 1H), 2.06–1.88 (m, 2H), 1.84- 1.74 (m, 1H), 1.57 (dt, J = 9.1, 1.4 Hz, 1H), 1.29 (dd, J = 7.5, 1.4 Hz, 3H), 1.27–1.09 (m, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 208.45, 208.41, 155.75, 152.20, 152.17, 149.95, 149.90, 136.59, 136.55, 115.13, 115.11, 114.36, 114.33, 48.39, 48.35, 44.42, 44.40, 44.34, 42.19, 42.14, 35.90, 35.87, 26.75, 26.73, 25.42, 25.38, 16.37, 16.34. [0232] 9-bromo-2-methyl-5,6,7,8-tetrahydro-1H-5,8-methanocyclopenta[b]naphthalene Solid sodium borohydride (1.39 g, 36.6 mmol) was added to a pre-cooled, stirring suspension of 4-bromo-2-methyl-2,3,5,6,7,8-hexahydro-1H-5,8-methanocyclopenta[b]naphthalen-1-one (3.56 g, 12.2 mmol) in methanol (50 mL) at 0°C. The reaction mixture was then stirred at room temperature for 90 minutes before being concentrated to ca 20 mL. Then, aqueous hydrochloric acid (1M, 50 mL) and diethyl ether (50 mL) were added. The obtained aqueous layer was separated and extracted with Et2O/EtOAc (1:1, 3 ^ 30 mL). The combined organic phase was subsequently washed with aqueous hydrochloric acid (1M, 50 mL), water (3 ^ 50 mL), and brine (2 ^ 50 mL), and finally dried over anhydrous MgSO4. Evaporation of the solvent afforded a light-yellow solid which was used for the next step without any purification. This intermediate product and catalytic amount of p-toluenesulfonic acid monohydrate (46 mg, 0.241 mmol) were dissolved in toluene (75 mL) and the obtained mixture was refluxed for 90 minutes. Then, toluene was evaporated to ca 10 mL of the reaction volume the mixture was transferred into a separatory funnel with water (50 mL). The aqueous layer was extracted with Et₂O/EtOAc (1:1, 3 ^ 40 mL) and the combined organic phase was subsequently washed with water (2 ^ 50 mL), aqueous Na₂CO₃ (2 ^ 50 mL), and brine (2 ^ 50 mL), and finally dried over anhydrous MgSO4. Evaporation of solvent gave a crude product which was purified by passing through a short silica plug using n-hexane/CH₂Cl₂ (3:1, v:v) as an eluent. The product was isolated as a light-yellow oil after evaporation of solvents. Overall yield over two steps: 3.27 g, 99%. ¹H NMR (500 MHz, CDCl3): δ 7.03 (s, 1H), 6.48 (h, J = 1.5 Hz, 1H), 3.60 (m, 1H), 3.47 (h, J = 1.5 Hz, 1H), 3.25 (d, J = 4.9 Hz, 2H), 2.18 (m, 3H), 2.00–1.90 (m, 2H), 1.82 (dp, J = 8.4, 2.0 Hz, 1H), 1.55 (dt, J = 8.7, 1.4 Hz, 1H), 1.32–1.15 (m, 2H). ¹³C NMR (126 MHz, CDCl3): δ 148.74, 145.37, 144.91, 143.30, 140.41, 127.30, 112.66, 111.73, 48.90, 44.98, 43.95, 43.84, 27.17, 26.29, 16.72. [0233] 9-(3,5-di-tert-Butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-5,8- methanocyclopenta[b]naphthalene 9-Bromo-2-methyl-5,6,7,8-tetrahydro-1H-5,8-methanocyclopenta[b]naphthalene (1.00 g, 3.63 mmol), (3,5-di-tert-butyl-4-methoxyphenyl)boronic acid (0.98 g, 4.00 mmol), K₂CO₃ (1.10 g, 7.99 mmol), bis(dibenzylideneacetone)palladium(0) (104 mg, 0.182 mmol), 1,3,5,7- tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (159 mg, 0.545 mmol) and THF (50 mL) were added to a pressure-resistant flask followed by degassed water (7 mL). The flask was sealed and heated with vigorous stirring at 80°C for 16 hours. Then, the flask was cooled to the ambient temperature and the reaction volume was reduced to ca 5 mL and water (20 mL) was added. The product was extracted into Et2O/EtOAc (1:1, 3 ^ 40 mL) and the combined organic phase was subsequently washed with water (3 ^ 50 mL), saturated sodium carbonate solution (2 ^ 50 mL) and brine (2 ^ 50 mL). The obtained organic phase was dried over MgSO4 and evaporated to give an orange solid. The product was further purified on Biotage automated column using silica gel and the mixture of ethyl acetate and n-hexane (7:93, v:v, respectively) as an eluent. Yield: 1.45 g (96%). ¹H NMR (500 MHz, CDCl₃): δ 7.38 (s, 2H), 7.12 (s, 1H), 6.52 (q, J = 1.6 Hz, 1H), 3.82 (s, 3H), 3.51–3.30 (m, 3H), 3.20 (d, J = 22.6 Hz, 1H), 2.15 (s, 3H), 2.03-1.96 (m, 2H), 1.83-1.80 (m, 1H), 1.56 (m, 1H), 1.53 (s, 18H), 1.46–1.29 (m, 2H). ¹³C NMR (126 MHz, CDCl₃): δ 158.03, 147.59, 145.00, 143.79, 142.84, 142.32, 138.61, 133.59, 131.78, 127.57, 127.33, 111.71, 64.13, 49.47, 44.33, 42.70, 42.26, 35.88, 32.31, 27.67, 27.45, 16.79. [0234] 9-(3,5-di-tert-Butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-5,8- methanocyclopenta[b]naphthalenyl)-lithium nBuLi (1.29 mL, 1.60 M in hexane, 2.07 mmol) was added dropwise to a precooled solution (-35°C) of 9-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-5,8- methanocyclopenta[b]naphthalene (0.78 g, 1.88 mmol) in Et₂O (40 mL). The resulting mixture was gradually warmed to the ambient temperature and the volatiles were evaporated. The resulting solid product was suspended in n-pentane (10 mL) and collected via filtration. The filtration cake was washed with n-pentane (3 ^ 5 mL) and dried in vacuo. Yield: 0.70 g, 89%. ¹H NMR (500 MHz, THF-d₈): δ 7.63 (s, 2H), 7.02 (s, 1H), 5.84 (d, J = 2.1 Hz, 1H), 5.75 (d, J = 2.2 Hz, 1H), 3.78 (s, 3H), 3.40–3.35 (m, 1H), 3.29–3.23 (m, 1H), 2.34 (s, 3H), 2.04–1.84 (m, 2H), 1.53 (s, 18H), 1.44–1.23 (m, 4H). ¹³C NMR (126 MHz, THF-d8): δ 156.62, 141.35, 137.10, 135.16, 132.11, 128.03, 127.46, 125.01, 124.30, 123.74, 109.25, 92.17, 91.75, 63.52, 48.14, 44.37, 42.40, 35.45, 31.87, 31.66, 29.16, 15.59. [0235] (4-(3,5-di-tert-Butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-5,8- methanocyclopenta[b]naphthalen-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1- yl)silane A solution of 9-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-5,8- methanocyclopenta[b]naphthalenyl)-lithium (0.400 g, 0.951 mmol) in diethyl ether (10 mL) and THF (0.25 mL) was added dropwise to a stirring solution of dimethyl(2,3,4,5- tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate (0.309 g, 0.942 mmol) in diethyl ether (10 mL) at -35°C. The reaction was allowed to warm up to ambient temperature and stirred for 14 hours. Then, the volatiles were removed, and the residue was dried under vacuum. The product was extracted into n-pentane (15 mL) and filtered through a short celite plug. Concentration under a stream of nitrogen and drying in vacuo afforded the product as an orange crude oil. It was used for the next step without any purification. Yield: 0.564 g (nearly 100%). [0236] Catalyst I6 nBuLi (1.25 mL, 1.6 M in hexane, 2.0 mmol) was added to a pre-cooled solution (-35°C) of (4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-5,6,7,8-tetrahydro-1H-5,8- methanocyclopenta[b]naphthalen-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1- yl)silane (564 mg, 0.951 mmol) in Et2O (10 mL). The mixture was allowed to warm up to the ambient temperature and stirred for additional 0.5 hour. The volatiles were then evaporated, and the resulting oily product was crystallized from the solution in n-pentane containing a few drops of Et2O at -35°C to give a yellow precipitate. It was dried in vacuo to give the product containing 1 eq of coordinated Et₂O according to ¹H NMR. Yield: 330 mg (51%). This intermediate product (314 mg, 0.464) was then suspended in Et₂O, cooled to -35°C. Then, solid ZrCl4 (110 mg, 0.470 mmol) was added. The mixture was stirred for 5 minutes and then the temperature was elevated to ambient. The mixture was stirred for 1 hour to give a yellow mixture. The solvent was then evaporated, and the obtained product was extracted into CH₂Cl₂ (3 mL). Filtration through a celite plug, evaporation and washing with n-pentane (3 x 5 mL) afforded a yellow powder after drying in vacuo. ¹H NMR spectroscopy and single-crystal X-ray diffraction study show the presence of two isomers (I6-a and I6-b) in the product with the molar ratio of ca 4:1, respectively. Yield: 290 mg (80% based on the dilithium salt). ¹H NMR (500 MHz, CDCl3) for I6-a and I6-b (in square brackets, not all signals observed due to overlapping with I6-a) δ 7.46 (s, 2H), 7.26 [7.23] (s, 1H), 6.77 [6.88] (s, 1H), [3.76] 3.78 (s, 3H), 3.50 [3.47] (m, 1H), 3.28 [3.22] (m, 1H), 2.24 [2.24] (s, 3H), [2.07] 2.05 (s, 3H), [2.02] 1.98 (s, 3H), 1.96 [1.94] (s, 3H), [1.93] 1.91 (s, 3H), 1.84 (m, 2H), 1.78 (m, 1H), 1.55 (m, 2H), [1.49] 1.49 (s, 18 H), 1.21 (s, 3H), 1.11 (m, 1H), 1.08 (s, 3H).¹³C NMR (126 MHz, CDCl3) δ 158.37, 146.98, 146.73, 142.99, 137.28, 134.54, 133.93, 133.17, 132.26, 129.62, 126.99, 128.10, 126.73, 124.41, 120.37, 114.05, 93.70, 82.45, 64.09, 46.69, 44.16, 41.61, 35.92, 32.30, 29.24, 26.93, 18.19, 15.96, 15.49, 12.55, 12.17, 3.24, 3.20. Syntheses of Catalysts I7 and I8 [0237] 2-Methyl-3,5,6,7,8,9-hexahydrocyclohepta[f]inden-1 -one A solution containing 6,7,8,9-tetrahydro-5H-benzo[7]annulene (16.8 g, 115 mmol, prepared according to the literature, J. Med. Chem. 2016, 59, 10, 4831) and 2-bromo-2-methyl- propanoyl bromide (26.4 g, 115 mmol) in dichloromethane (50 mL) was added over 30 minutes to the stirred suspension of AlCl3 (38.3 g, 288 mmol) in dichloromethane (200 mL) at 0°C. After the addition was completed, the reaction mixture was allowed to warm to the ambient temperature and stirred for 16 hours. Then, the reaction mixture was transferred to a separatory funnel containing ice. The organic layer was separated, and the residual aqueous layer was extracted with CH₂Cl₂ (2 ^ 50 mL). The combined organic phase was subsequently washed with 1M hydrochloric acid (50 mL), water (100 mL), aqueous NaHCO3 (100 mL), and brine (2 ^ 100 mL) before drying over MgSO4. The evaporation of solvent gave an oily product which was heated at 125°C under reduced pressure (500 mtorr) for 2 hours. The obtained yellow oil was dissolved in isohexane (20 mL) and stored at -35°C for 3 days. The formed light-yellow crystals were collected via filtration, washed with cold n-hexane (2 ^ 10 mL) and dried in vacuo. Yield: 9.98 g (41%). ¹H NMR (400 MHz, CDCl3): δ 7.50 (s, 1H), 7.19 (s, 1H), 3.41–3.26 (m, 1H), 2.87 (td, J = 6.9, 3.5 Hz, 4H), 2.76–2.59 (m, 2H), 1.86 (p, J = 5.9 Hz, 2H), 1.74–1.57 (m, 4H), 1.31 (d, J = 7.1 Hz, 3H).¹³C NMR (101 MHz, CDCl3): δ 209.32, 152.08, 151.69, 143.20, 134.55, 126.71, 123.72, 42.24, 37.18, 36.30, 34.62, 32.43, 28.34, 28.14, 16.45. [0238] 4-Bromo-2-methyl-3,5,6,7,8,9-hexahydrocyclohepta[f]inden-1 -one Under the nitrogen atmosphere, a cold solution (0°C) of 2-methyl-3,5,6,7,8,9- hexahydrocyclohepta[f]inden-1(2H)-one (3.80 g, 17.7 mmol) in CH₂Cl₂ (20 mL) was slowly added under stirring to the solution of AlBr₃ (13.1 g, 49.1 mmol) in CH₂Cl₂ (40 mL) at 0°C. The resulting mixture was stirred for 1 hour at 0°C before the solution of Br2 (3.37 g, 21.1 mmol) in CH2Cl2 (25 mL) was added over 45 minutes at 0°C. The temperature of the reaction mixture was gradually increased to 25°C and the mixture was stirred for 17 hours. Then, the obtained mixture was poured into ice water (100 mL), and the formed organic layer was separated. The aqueous layer was extracted with CH2Cl2 (3 ^ 30 mL) and the combined organic layer was subsequently washed with aqueous Na2CO3 (100 mL), water (2 ^ 50 mL), and brine (2 ^ 50 mL). The combined organic layer was then dried over MgSO4, filtered and evaporated. The obtained crude product was purified by passing through a short silica plug using n-hexane/CH2Cl2 (2:1, v:v) as an eluent. The product was isolated as a yellow oil after evaporation of solvents. Yield: 4.51 g (88%). ¹H NMR (400 MHz, CDCl₃): δ 7.44 (s, 1H), 3.33 (dd, J = 17.5, 7.7 Hz, 1H), 3.22–3.14 (m, 2H), 2.96–2.89 (m, 2H), 2.73 (pd, J = 7.5, 3.8 Hz, 1H), 2.64 (dd, J = 17.5, 3.8 Hz, 1H), 1.93–1.79 (m, 2H), 1.72–1.61 (m, 4H), 1.33 (d, J = 7.5 Hz, 3H).¹³C NMR (101 MHz, CDCl₃): δ 208.82, 152.28, 150.10, 145.34, 135.74, 123.72, 122.54, 42.28, 37.22, 36.68, 34.23, 31.88, 28.02, 26.52, 16.34. [0239] 10-Bromo-2-methyl-1,5,6,7,8,9-hexahydrocyclohepta[f]indene Solid sodium borohydride (1.75 g, 46.1 mmol) was added to a pre-cooled, stirring suspension of 4-bromo-2-methyl-3,5,6,7,8,9-hexahydrocyclohepta[f]inden-1(2H)-one (4.51 g, 15.4 mmol) in methanol (75 mL) at 0°C. The reaction mixture was then stirred at room temperature for 90 minutes before being concentrated to ca 20 mL. Then, aqueous hydrochloric acid (1M, 100 mL), diethyl ether (50 mL) and ethylacetate (50 mL) were added. The obtained aqueous layer was separated and extracted with Et2O/EtOAc (1:1, 3 ^ 30 mL). The combined organic phase was subsequently washed with aqueous hydrochloric acid (1M, 100 mL), water (2 ^ 50 mL), and brine (2 ^ 50 mL), and finally dried over anhydrous MgSO4. Evaporation of the solvent afforded a light-yellow powder which was used for the next step without any purification. This intermediate product and catalytic amount of p-toluenesulfonic acid monohydrate (58.5 mg, 0.308 mmol) were dissolved in toluene (75 mL) and the obtained mixture was refluxed for 90 minutes. Then, toluene was evaporated to ca 10 mL of the reaction volume the mixture was transferred into a separatory funnel with water (50 mL). The aqueous layer was extracted with Et2O/EtOAc (1:1, 3 ^ 40 mL) and the combined organic phase was subsequently washed with water (2 ^ 50 mL), aqueous Na2CO3 (2 ^ 50 mL), and brine (2 ^ 50 mL), and finally dried over anhydrous MgSO4. Evaporation of solvent gave a crude product which was purified by passing through a short silica plug using n-hexane/CH₂Cl₂ (3:1, v:v) as an eluent. The product was isolated as a light-yellow solid after evaporation of solvents. Overall yield over two steps: 4.20 g, 99%. ¹H NMR (500 MHz, CDCl3): δ ¹H NMR (400 MHz, CDCl3): δ 6.97 (s, 1H), 6.46 (h, J = 1.5 Hz, 1H), 3.29 (s, 2H), 3.15–3.09 (m, 2H), 2.90–2.85 (m, 2H), 2.17 (s, 3H), 1.90–1.82 (m, 2H), 1.67 (dq, J = 11.1, 5.8 Hz, 4H).¹³C NMR (126 MHz, CDCl3): δ 146.24, 144.28, 143.82, 141.72, 137.29, 126.85, 120.76, 119.71, 45.54, 37.11, 33.44, 32.31, 28.39, 27.28, 16.72. [0240] 10-(3,5-di-tert-Butyl-4-methoxyphenyl)-2-methyl-1,5,6,7,8,9- hexahydrocyclohepta[f]indene 10-Bromo-2-methyl-1,5,6,7,8,9-hexahydrocyclohepta[f]indene (1.00 g, 3.61 mmol), (3,5-di- tert-butyl-4-methoxyphenyl)boronic acid (1.31 g, 3.79 mmol), K2CO3 (1.10 g, 7.94 mmol), bis(dibenzylideneacetone)palladium(0) (104 mg, 0.180 mmol), 1,3,5,7-tetramethyl-6-phenyl- 2,4,8-trioxa-6-phosphaadamantane (158 mg, 0.541 mmol) and THF (25 mL) were added to a pressure-resistant flask followed by degassed water (4 mL). The flask was sealed and heated with vigorous stirring at 80°C for 14 hours. Then, the flask was cooled to the ambient temperature and the reaction volume was reduced to ca 10 mL and diluted with water (50 mL). The product was extracted into Et2O/EtOAc (1:1, 3 ^ 30 mL) and the combined organic phase was subsequently washed with water (3 ^ 50 mL), saturated sodium carbonate solution (2 ^ 50 mL) and brine (2 ^ 50 mL). The obtained organic phase was dried over MgSO4 and evaporated to give an orange oil. The product was dissolved in the CH2Cl2/n-hexane mixture (1:4, v:v, respectively) and passed through a short silica gel plug. The solvent was evaporated and the product was further purified on Biotage automated column using silica gel and the mixture of ethyl acetate and n-hexane (5:95, v:v, respectively) as an eluent. Yield: 0.69 g (46%). ¹H NMR (400 MHz, CDCl3): δ 7.15 (s, 2H), 7.07 (s, 1H), 6.48 (h, J = 1.6 Hz, 1H), 3.78 (s, 3H), 3.06 (s, 2H), 2.95–2.87 (m, 2H), 2.68–2.61 (m, 2H), 2.11 (s, 3H), 1.89-1.83 (m, 2H), 1.76-1.71 (m, 2H), 1.66–1.58 (m, 2H), 1.48 (s, 18H).¹³C NMR (126 MHz, CDCl₃): δ 157.84, 146.00, 143.06, 142.88, 142.63, 140.35, 137.80, 136.75, 135.00, 127.66, 126.89, 119.70, 64.18, 43.20, 37.05, 35.86, 32.70, 32.36, 31.16, 28.73, 28.59, 16.84. [0241] 10-(4-(tert-Butyl)phenyl)-2-methyl-1,5,6,7,8,9-hexahydrocyclohepta[f]indene 10-Bromo-2-methyl-1,5,6,7,8,9-hexahydrocyclohepta[f]indene (0.90 g, 3.25 mmol), (4-tert- butylphenyl)boronic acid (0.64 g, 3.57 mmol), K2CO3 (0.99 g, 7.14 mmol), bis(dibenzylideneacetone)palladium(0) (93.3 mg, 0.162 mmol), 1,3,5,7-tetramethyl-6-phenyl- 2,4,8-trioxa-6-phosphaadamantane (142 mg, 0.487 mmol) and THF (25 mL) were added to a pressure-resistant flask followed by degassed water (4 mL). The flask was sealed and heated with vigorous stirring at 80°C for 14 hours. Then, the flask was cooled to the ambient temperature and the reaction volume was reduced to ca 10 mL. Water (50 mL) was added, and the product was extracted into Et2O/EtOAc (1:1, 3 ^ 30 mL). The combined organic phase was subsequently washed with water (3 ^ 50 mL), saturated sodium carbonate solution (2 ^ 50 mL) and brine (2 ^ 50 mL). The obtained organic phase was dried over MgSO4 and evaporated to give a red oil. The product was purified on Biotage automated column using silica gel and the mixture of ethyl acetate and n-hexane (5:95, v:v, respectively) as an eluent. Yield: 0.778 g of a colorless solid (73%). ¹H NMR (400 MHz, CDCl₃): δ 7.45 (d, J = 8.3 Hz, 2H), 7.19 (d, J = 8.3 Hz, 2H), 7.08 (s, 1H), 6.50–6.41 (m, 1H), 3.04 (s, 2H), 2.95–2.86 (m, 2H), 2.69–2.60 (m, 2H), 2.09 (s, 3H), 1.87-1.81 (m, 2H), 1.75-1.70 (m, 2H), 1.60-1.55 (m, 2H), 1.42 (s, 9H). ¹³C NMR (101 MHz, CDCl₃): δ 149.13, 146.06, 142.94, 142.45, 140.47, 137.99, 137.04, 136.69, 128.80, 126.75, 124.99, 119.81, 43.08, 37.05, 34.56, 32.61, 31.50, 31.01, 28.63, 28.46, 16.78. [0242] 10-(3,5-di-tert-Butyl-4-methoxyphenyl)-2-methyl-5,6,7,8,9- pentahydrocyclohepta[f]indenyl] lithium nBuLi (1.09 mL, 1.6 M, 1.74 mmol) was added to the solution of 10-(3,5-di-tert-butyl-4- methoxyphenyl)-2-methyl-1,5,6,7,8,9-hexahydrocyclohepta[f]indene (690 mg, 1.66 mmol) in Et2O (10 mL) at -35°C under stirring. The resulting mixture was allowed to warm up to ambient temperature to give an orange solution with a yellow precipitate. After stirring for 1 hour at ambient temperature, the volatiles were evaporated, and n-pentane (10 mL) was added. A yellow solid product was collected on a filter disk, washed several times with n-pentane (20 mL) and dried in vacuo. Yield: 0.562 g (76%). ¹H NMR (400 MHz, THF-d8): δ 7.36 (s, 2H), 7.02 (s, 1H), 5.69 (d, J = 2.1 Hz, 1H), 5.44 (m, 1H), 3.78 (s, 3H), 2.97–2.79 (m, 2H), 2.79–2.58 (m, 2H), 2.29 (s, 3H), 1.89–1.59 (m, 4H), 1.51 (s, 18H), 1.40–1.20 (m, 2H). ¹³C NMR (101 MHz, THF-d8): δ 157.62, 142.10, 139.42, 131.15, 130.26, 129.85, 128.20, 128.11, 126.44, 126.33, 118.65, 93.47, 92.15, 64.51, 38.86, 36.35, 32.86, 32.67, 32.52, 31.76, 31.65, 16.54. [0243] 10-(4-(tert-Butyl)phenyl)-2-methyl-5,6,7,8,9-pentahydrocyclohepta[f]indenyl] lithium nBuLi (1.54 mL, 1.6 M, 2.46 mmol) was added to the solution of 10-(4-(tert-butyl)phenyl)-2- methyl-1,5,6,7,8,9-hexahydrocyclohepta[f]indene (775 mg, 2.34 mmol) in Et₂O (10 mL) at - 40°C under stirring. The resulting mixture was allowed to warm up to ambient temperature to give an orange solution with a yellow precipitate. After stirring for 1 hour at ambient temperature, the volatiles were evaporated, and n-pentane (10 mL) was added. A yellow solid product was collected on a filter disk, washed several times with n-pentane (20 mL) and dried in vacuo. The compound was isolated as a salt with 0.75 equiv. of Et2O. Yield: 0.510 g (56%). ¹H NMR (400 MHz, THF-d₈): δ 7.40 (d, J = 8.3 Hz, 2H), 7.32 (d, J = 8.3 Hz, 2H), 7.03 (s, 1H), 5.69 (d, J = 2.2 Hz, 1H), 5.36 (d, J = 2.1 Hz, 1H), 3.43 (q, J = 7.0 Hz, 3H), 2.92–2.76 (m, 2H), 2.76–2.58 (m, 2H), 2.28 (s, 3H), 1.87–1.66 (m, 2H), 1.60 (m, 2H), 1.42 (s, 9H), 1.39-1.33 (m, 2H), 1.16 (t, J = 7.0 Hz, 4.5H). [0244] (4-(3,5-di-tert-Butyl-4-methoxyphenyl)-2-methyl-1,5,6,7,8,9- hexahydrocyclohepta[f]inden-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1- yl)silane

To a stirring solution of dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate (411 mg, 1.25 mmol) in diethyl ether (10 mL) was added a suspension of 10-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-5,6,7,8,9- pentahydrocyclohepta[f]indenyl] lithium (534 mg, 1.26 mmol) in diethyl ether (5 mL) at -35°C. The reaction was allowed to warm up to ambient temperature and stirred for 90 minutes. Then, the reaction was concentrated under a stream of nitrogen and the resulting residue was dried under vacuum. The product was extracted into n-pentane (2 x 20mL) and filtered through celite plug. Concentration under a stream of nitrogen and drying in vacuo afforded the product as a white foam. Yield: 705 mg (95%). ¹H NMR (400 MHz, C₆D₆): δ 7.52 (d, J = 2.2 Hz, 1H), 7.46 (d, J = 2.2 Hz, 1H), 7.35 (s, 1H), 6.60 (t, J = 1.5 Hz, 1H), 3.65 (s, 1H), 3.51 (s, 3H), 3.23 (s, 1H), 3.05–2.68 (m, 4H), 1.99 (s, 3H), 1.98 (s, 3H), 1.91 (s, 3H), 1.82 (m, 6H), 1.79 – 1.60 (m, 6H), 1.54 (s, 9H), 1.52 (s, 9H), -0.13 (s, 3H), -0.18 (s, 3H). ¹³C NMR (101 MHz, C₆D₆): δ 158.01, 145.69, 143.09, 142.82, 142.78, 142.72, 138.77, 137.65, 136.29, 136.20, 135.65, 134.14, 134.81, 134.75, 129.03, 128.86, 127.07, 123.26, 63.75, 47.65, 37.35, 35.68, 35.65, 34.07, 32.47, 32.20, 32.16, 31.24, 29.14, 28.87, 22.35, 17.66, 14.70, 14.62, 13.90, 11.07, -5.45, -5.58. [0245] [4-(4-tert-Butylphenyl)-2-methyl-1,5,6,7,8,9-hexahydrocyclohepta[f]inden-1-yl]- dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane To a stirring solution of dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate (423 mg, 1.29 mmol) in diethyl ether (10 mL) was added a suspension of [10-(4-(tert-butyl)phenyl)-2-methyl-5,6,7,8,9-pentahydrocyclohepta[f]indenyl] lithium (510 mg, 1.30 mmol, adduct with 0.75 equiv. of Et2O) in diethyl ether (5 mL) at -30°C. The reaction was allowed to warm up to ambient temperature and stirred for 90 minutes. Then, the reaction was concentrated under a stream of nitrogen and the resulting residue was dried under vacuum. The product was extracted into n-pentane (2 x 20mL) and filtered through celite plug. Concentration under a stream of nitrogen and drying in vacuo afforded the product as a white foam. Yield: 621 mg (94%). ¹H NMR (400 MHz, C₆D₆): δ 7.43 (m, 2H), 7.41–7.36 (m, 2H), 7.33 (s, 1H), 6.45 (m, 1H), 3.62 (s, 1H), 3.24 (s, 1H), 3.06–2.83 (m, 2H), 1.98 (s, 3H), 1.97 (s, 3H), 1.92 (s, 3H), 1.83 (m, 6H), 1.82 – 1.71 (m, 2H), 1.71–1.48 (m, 4H), 1.30 (s, 9H), 1.27– 1.16 (m, 2H), -0.14 (s, 3H), -0.18 (s, 3H).¹³C NMR (101 MHz, C₆D₆): δ 148.81, 145.51, 143.13, 142.61, 138.62, 137.59, 136.30, 136.18, 133.45, 130.14, 129.82, 127.06, 124.98, 124.87, 123.39, 47.54, 37.32, 34.24, 31.60, 31.25, 31.08, 29.08, 28.63, 22.68, 17.56, 14.71, 14.63, 13.98, 11.07, -5.43, -5.58. [0246] nBuLi (1.28 mL, 1.6 M in hexane, 2.04 mmol) was added dropwise to a precooled solution (-30°C) of [4-(3,5-di-tert-butyl-4-methoxy-phenyl)-2-methyl-1,5,6,7,8,9- hexahydrocyclohepta[f]inden-1-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1- yl)silane (705 mg, 0.972 mmol) in Et2O (15 mL). The mixture was allowed to warm up to the ambient temperature under stirring over 1 hour. The resulting white suspension was cooled back to -30°C before solid (Et₂O)₂ZrCl₄ (408 mg, 1.07 mmol) was added in small portions over 10 minutes. The mixture was stirred for 10 minutes at -30°C and then the reaction mixture was gradually warmed up to ambient temperature. Additional stirring for 1 hour gave a yellow precipitate. Volatiles were then evaporated, and the product was extracted into toluene (15 mL). Filtration through a celite plug and evaporation of the solvent gave an orange oil which was dissolved in n-pentane and filtered from small amounts of insoluble residues. Evaporation of the solvent afforded a bright yellow solid which was collected by filtration and washed with n-pentane (2 mL). The product was dried in vacuo. Yield: 416 mg (57%). ¹H NMR (400 MHz, CDCl₃) δ 7.70 (d, J = 2.2 Hz, 1H), 7.31 (s, 1H), 7.03 (d, J = 2.2 Hz, 1H), 6.50 (s, 1H), 3.79 (s, 3H, OCH3), 2.97–2.59 (m, 4H), 2.24 (s, 3H), 2.08 (s, 3H), 2.03 (s, 3H), 1.99 (s, 3H), 1.97 (s, 3H), 1.77–1.67 (m, 4H), 1.50 (s, 9H, tBu), 1.47 (s, 9H, tBu), 1.42 – 1.29 (m, 2H), 1.23 (s, 3H), 1.10 (s, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 158.17, 143.30, 142.47, 142.37, 141.18, 137.40, 135.49, 135.41, 134.42, 133.85, 133.56, 128.61, 127.73, 127.02, 126.95, 123.70, 122.51, 121.04, 93.83, 81.94, 64.11, 37.73, 36.11, 35.72, 32.40, 32.26, 32.05, 31.26, 30.15, 28.94, 18.14, 15.89, 15.52, 12.58, 12.19, 3.18. [0247] Catalyst I8 nBuLi (1.60 mL, 1.6 M in hexane, 2.56 mmol) was added dropwise to a precooled solution (-30°C) of [4-(4-tert-butylphenyl)-2-methyl-1,5,6,7,8,9-hexahydrocyclohepta[f]inden-1-yl]- dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (621 mg, 1.22 mmol) in Et2O (15 mL). The mixture was allowed to warm up to the ambient temperature under stirring over 1 hour. The resulting white suspension was cooled back to -30°C before solid (Et₂O)₂ZrCl₄ (512 mg, 1.34 mmol) was added in small portions over 10 minutes. The mixture was stirred for 10 minutes at -30°C and then the reaction mixture was gradually warmed up to ambient temperature. Additional stirring for 1 hour gave a yellow precipitate. Volatiles were then evaporated, and the product was extracted into dichloromethane (15 mL). Filtration through a celite plug and evaporation of the solvent gave an orange oil which was suspended in n-pentane (15 mL). The obtained solid product was collected via filtration and washed with n-pentane (2 mL). Further purification was achieved by dissolving the product in toluene/CHCl₃ (4:1, v:v) and filtration from insolubles through a short celite plug. Evaporation of the solvent and drying in vacuo afforded a yellow solid. Yield: 496 mg (61%). ¹H NMR (400 MHz, CDCl3) δ ¹H NMR (400 MHz, CDCl₃): δ 7.70 (dd, J = 8.1, 1.9 Hz, 1H), 7.49 (dd, J = 8.1, 2.1 Hz, 1H), 7.42 (dd, J = 8.0, 2.1 Hz, 1H), 7.31 (s, 1H), 7.09 (dd, J = 8.1, 1.9 Hz, 1H), 6.52 (s, 1H), 2.91– 2.64 (m, 4H), 2.22 (s, 3H), 2.07 (s, 3H), 2.01 (s, 3H), 1.99 (s, 3H), 1.97 (s, 3H), 1.86–1.53 (m, 6H), 1.41 (s, 9H), 1.23 (s, 3H), 1.10 (s, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 149.54, 142.39, 141.45, 137.56, 136.43, 135.21, 134.87, 134.54, 133.85, 129.25, 129.16, 127.17, 127.03, 125.42, 124.60, 123.76, 122.73, 121.19, 93.70, 81.75, 37.72, 34.59, 32.00, 31.47, 31.13, 30.10, 28.82, 18.03, 15.87, 15.50, 12.60, 12.15, 3.17. Preparation of support material (SMAO) [0248] 12.8 g of PD17062 silica (600°C calcination) was slurried in 50 mL of toluene and cooled to -35°C in the freezer. While stirring, 21.0 g of MAO (30% solution in toluene) was then added slowly via pipette. The mixture was allowed to warm up to room temperature and was stirred for 1 hour. After 1 hour, the mixture was heated to 100°C for additional 2.5 hours. After 2.5 hours, the mixture was cooled to 55°C and filtered while hot. The collected solid was washed with toluene (2 x 30 mL) and pentane (2 x 30 mL) and dried in vacuo to afford 18.2 g of SMAO as a white free flowing powder. Preparation of supported catalysts I1 and I2. [0249] 1 g of SMAO was placed in 6 mL of toluene and placed on a shaker. While shaking, 0.52 mL of 1M solution of triisobutylaluminum was added. The mixture was allowed to shake for 15 minutes at room temperature. After 15 minutes, 22 µmol of metallocene I1 or I2 was added in ca 2 mL of toluene. The reaction mixture was allowed to shake for 3.5 hours. After 3.5 hours, the slurry was filtered, and the solid was washed with toluene (2 x 5 mL) and hexane (2 x 5 mL) and dried in vacuo. Each catalyst was used in reactor testing as 5 wt% slurry in mineral oil. Propylene polymerization in a 2L reactor. [0250] A 2L autoclave equipped with a steam jacket and mechanical stirrer was nitrogen purged and heated to 130°C for at least 1 hour. Upon cooling to room temperature, liquid propylene (600 mL), triisobutylaluminum (0.4 mL of 1M solution in hexane) and desired amount of hydrogen (typically 1 – 30 mmol) were added and allowed to mix for 5 minutes. After 5 minutes, catalyst slurry (typically 12.5 – 25.0 mg of dry catalyst) was flushed in the reactor along with 200 mL of liquid propylene. The contents of the reactor were allowed to mix for 5 minutes (pre-polymerization stage), before reactor temperature was raised to 70°C to start the polymerization. After 30 minutes, the reactor was cooled to room temperature, unreacted propylene was vented, and the polymer was collected and allowed to dry overnight. Gel Permeation Chromotography [0251] High temperature size exclusion chromatography was performed on samples described in Table 1 using an automated "Rapid GPC" system as described in U.S. Patent Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388; each of which is incorporated herein by reference. Molecular weights (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distribution (MWD = Mw/Mn), which is also sometimes referred to as the polydispersity index (PDI) of the polymer, were measured by Gel Permeation Chromatography using a Symyx Technology GPC equipped with evaporative light scattering detector (ELSD) and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit S-M-10: Mp (peak Mw) between 5000 and 3,390,000). Alternatively, samples were measured by Gel Permeation Chromatography using a Symyx Technology GPC equipped with dual wavelength infrared detector and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit S-M-10: Mp (peak Mw) between 580 and 3,039,000). Samples (250 μL of a polymer solution in TCB were injected into the system) were run at an eluent flow rate of 2.0 mL/minute (135°C sample temperatures, 165°C oven/columns) using three Polymer Laboratories: PLgel 10μm Mixed-B 300 x 7.5mm columns in series. No column spreading corrections were employed. Numerical analyses were performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. The molecular weights obtained are relative to linear polystyrene standards. GPC-4D [0252] Unless otherwise indicated the reactor samples were analyzed according to the GPC- 4D method described above. Differential Scanning Calorimetry (DSC) [0253] Peak melting point, Tm, described for larger scale reactor batches (also referred to as melting point) and peak crystallization temperature, T_c, (also referred to as crystallization temperature) are determined using the following DSC procedure. Differential scanning calorimetric (DSC-2) data can be obtained using a TA Instruments model DSC2500 machine. Samples weighing approximately 5 to 10 mg are sealed in an aluminum hermetic sample pan and loaded into the instrument at about room temperature. The DSC data are recorded by first gradually heating the sample to 220°C at a rate of 10°C/minute in order to erase all thermal history. The sample is kept at 220°C for 5 minutes, then cooled to -10°C at a rate of 10°C/minute, followed by an isothermal for 5 minutes and heating to 220°C at 10°C/minute, holding at 220°C for 5 minutes and then cooling down to 25°C at a rate of 10°C/minute. Both the first and second cycle thermal events were recorded. The melting and crystallization temperatures reported here were obtained during the second heating/cooling cycle unless otherwise noted. [0254] Overall, catalyst compounds of the present disclosure can have 2-substituted 5,6,7,8- tetrahydro-cyclopenta[b]naphthalenyl moieties. It has been discovered that catalysts of the present disclosure can exhibit excellent activities, provide high melting points, and have broad molecular weight capabilities particularly for propylene polymerization. Relative to indacenyl and tetrahydroindacenyl catalyst systems, catalyst compounds of the present disclosure show significant improvement in supported catalyst activities in preparation of isotactic polypropylene having high melt temperature and improved stiffness, broad MFR, and narrow polydispersities. The combination of such polymer properties allows for preparation of polymers applicable in large markets such as hygiene (fibers and injection molding products), rigid and flexible packaging, and automotive applications. [0255] In addition to improved operability, it has been discovered that broad polymer product capability can be achieved. For example, polymers of the present disclosure can have narrow polydispersity, robust isotacticity, and broad melt flow rate (MFR) capability (provided by broad hydrogen response of the catalyst used for polymerization). High MFR can be provided by high hydrogen loading in the reactor, which catalysts of the present disclosure are amenable to. [0256] Higher activity achieved while maintaining relatively comparable molecular weight capability and narrow polydispersities (PDI) represents a clear advantage of using catalyst systems based on 5,6,7,8-tetrahydro-cyclopenta[b]naphthalenyl groups. Such molecular weight capability range corresponds to a broad MFR range (1 – 1000 MFR), thus significantly extending the applicability of ansa-metallocene catalysts. In addition, catalysts tested were able to maintain narrow MWD while eliminating higher fractions of low molecular weight tails. Such benefit allows for preparation of resins for fiber spinning (spunbound and meltblown) and injection molding articles used in medical applications, which involve cleanliness, narrow polydispersities, low volatile organic compounds (VOCs) and low odor. In addition, high melting points of polypropylenes provided by catalyst compounds of the present disclosure allows for improved stiffness for rigid parts, allowing application of polypropylene for impact copolymer compositions used in automotive industry. For example, polypropylenes of the present disclosure can have reduced defects which provides such improved stiffness (e.g., provided by 5,6,7,8-tetrahydro-cyclopenta[b]naphthalenyl of the catalyst compounds). In addition to improved stiffness, polypropylenes can have significantly improved tensile properties, especially at higher hydrogen loadings (and thus polymer MFR). [0257] The phrases, unless otherwise specified, "consists essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the present disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used. [0258] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited. [0259] All documents described herein are incorporated by reference herein, including any priority documents and or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including” for purposes of United States law. Likewise, whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa. While the present disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure.

Claims

CLAIMS: We claim: 1. A process for producing propylene homopolymer or copolymer, the process comprising: polymerizing propylene and optionally one or more comonomers selected from the group consisting of one or more C2 or C4-C20 alpha-olefins, by introducing the propylene, optionally the one or more C₂ or C₄-C₂₀ alpha-olefins, and optionally hydrogen, with a catalyst system comprising a catalyst compound and an activator, in solution, gas phase, or slurry reactor, in series, or in parallel, at a reactor pressure of about 0.05 MPa to about 1,500 MPa and a reactor temperature of about 30°C to about 230°C to form the propylene homopolymer or copolymer, wherein the catalyst compound is represented by Formula (I): (I) wherein: M is a group 3 metal, group 4 metal, or group 5 metal; T is a bridging group; each of X¹ and X² is independently a univalent anionic ligand, or X¹ and X² are joined to form a metallocycle ring; R¹, R², R³, and R⁴ are each independently hydrogen or substituted or unsubstituted C₁ to C6 hydrocarbyl group and, optionally, any adjacent R¹, R², R³ and R⁴ can be joined to form a cyclic structure; R⁵ is a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group; R⁶ and R⁸ are each independently hydrogen or a substituted or unsubstituted C1 to C20 hydrocarbyl group; R⁷ is a substituted aryl group, an unsubstituted naphthyl group, an unsubstituted anthracenyl group, or a substituted or unsubstituted heteroaryl group; and 114

R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently hydrogen or a substituted or unsubstituted C1 to C20 hydrocarbyl group, wherein optionally R⁹ and R¹¹ combine to form a substituted or unsubstituted divalent methylene, divalent ethylene or divalent hydrocarbyl group.

2. The method of claim 1, wherein each of R¹, R², R³, and R⁴ is methyl.

3. The method of claim 2, wherein: R⁵ is C1-C3 alkyl, and each of R⁶ and R⁸ is hydrogen.

4. The method of claim 3, wherein R⁷ is a substituted aryl group represented by the formula: , wherein each of R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is independently hydrogen, hydrocarbyl, a heteroatom, or heteroatom-containing group, wherein at least one of R¹⁷, R¹⁸, R¹⁹, R²⁰, or R²¹ is not hydrogen, or one or more of R¹⁷ and R¹⁸, R¹⁸ and R¹⁹, R¹⁹ and R²⁰, or R²⁰ and R²¹ are joined to form a completely saturated, partially saturated, or aromatic ring.

5. The method of claim 4, wherein R⁷ is selected from the group consisting of:

6. The method of claim 1, wherein each of R⁹, R¹⁰, R¹¹, and R¹² is independently hydrogen.

7. The method of claim 6, wherein T is selected from the group consisting of Si(CH₃)₂, Si(CH2CH3)2, and Si(CH2CH2CH3)2.

8. The method of claim 7, wherein M is zirconium or hafnium. 115

9. The method of claim 8, wherein each of X¹ and X² is chloro.

10. The method of claim 1, wherein: (1) M is zirconium or hafnium, (2) T is Si(CH3)2, Si(CH2CH3)2, or Si(CH2CH2CH3)2, (3) each of R⁶ and R⁸ is hydrogen or unsubstituted C₁-C₁₀ alkyl, (4) each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ is hydrogen, (5) each of R¹, R², R³, and R⁴ is independently methyl, ethyl, or propyl, (6) R⁵ is C1-C10 alkyl, (7) R⁷ is substituted aryl, and (8) each of X¹ and X² is independently chloro or methyl.

11. The catalyst compound of claim 1, wherein the catalyst compound is selected from the group consisting of: 116

117

118

119

12. The method of claim 11, wherein the propylene homopolymer or copolymer has each of the following properties: (1) an average meso run length of about 98 or greater, (2) an [mmmm] pentad content of about 95.0% to about 99.5%, (3) a melting point (Tm) of about 157°C to about 159°C, and (4) a weight average molecular weight (Mw) of about 150,000 g/mol or greater.

13. A catalyst compound represented by Formula (IIa) or (IIb): 120

wherein: M of Formula (IIa) or (IIb) is a group 3 metal, group 4 metal, or group 5 metal; T of Formula (IIa) or (IIb) is a bridging group; each of X¹ and X² of Formula (IIa) or (IIb) is independently a univalent anionic ligand, or X¹ and X² are joined to form a metallocycle ring; R¹, R², R³, and R⁴ of Formula (IIa) or (IIb) are each independently hydrogen or substituted or unsubstituted C1 to C6 hydrocarbyl group and, optionally, any adjacent R¹, R², R³ and R⁴ can be joined to form a cyclic structure; R⁵ of Formula (IIa) or (IIb) is a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group; R⁶ and R⁸ of Formula (IIa) or (IIb) are each independently hydrogen or a substituted or unsubstituted C1 to C20 hydrocarbyl group; R⁷ of Formula (IIa) or (IIb) is a substituted aryl group, unsubstituted naphthyl, unsubstituted anthracenyl, or substituted or unsubstituted heteroaryl group; R⁹ and R¹⁰ of Formula (IIa) or (IIb) are each independently hydrogen or a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group; R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently hydrogen or a substituted or unsubstituted C1 to C20 hydrocarbyl group; each instance of R¹¹ and R¹² of Formula (IIa) or (IIb) is independently hydrogen or a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group, and n is 1 or 2 for Formula (IIa) and m is 1 for Formula (IIb). 121

14. The catalyst compound of claim 13, wherein each of R¹, R², R³, and R⁴ of Formula (IIa) or (IIb) is methyl.

15. The catalyst compound of claims 13 or 14, wherein each of R⁵ _, R⁶, and R⁸ of Formula (IIa) or (IIb) is independently a C1-C3 alkyl.

16. The catalyst compound of any of claims 13 to 15, wherein each of R⁶ and R⁸ of Formula (IIa) or (IIb) is hydrogen.

17. The catalyst compound of any of claims 13 to 16, wherein R⁷ of Formula (IIa) or (IIb) is a substituted aryl group represented by the formula: , wherein each of R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is independently hydrogen, hydrocarbyl, a heteroatom, or heteroatom-containing group, wherein at least one of R¹⁷, R¹⁸, R¹⁹, R²⁰, or R²¹ is not hydrogen, or one or more of R¹⁷ and R¹⁸, R¹⁸ and R¹⁹, R¹⁹ and R²⁰, or R²⁰ and R²¹ are joined to form a completely saturated, partially saturated, or aromatic ring.

18. The catalyst compound of any of claims 13 to 17, wherein R⁷ of Formula (IIa) or (IIb) is selected from the group consisting of:

19. The catalyst compound of any of claims 13 to 18, wherein each of R⁹, R¹⁰, R¹¹, and R¹² of Formula (IIa) or (IIb) is hydrogen.

20. The catalyst compound of any of claims 13 to 19, wherein: T of Formula (IIa) or (IIb) is selected from the group consisting of Si(CH3)2, Si(CH₂CH₃)₂, and Si(CH₂CH₂CH₃)₂, M of Formula (IIa) or (IIb) is zirconium or hafnium, and each of X¹ and X² of Formula (IIa) or (IIb) is chloro or methyl. 122

21. The catalyst compound of claim 13, wherein for Formula (IIa) or (IIb): (1) M is zirconium or hafnium, (2) T is Si(CH₃)₂, Si(CH₂CH₃)₂, or Si(CH₂CH₂CH₃)₂, (3) each of R⁶ and R⁸ is independently hydrogen or unsubstituted C1-C10 alkyl, (4) each of R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ is independently hydrogen, (5) each of R¹, R², R³, and R⁴ is independently methyl, ethyl, or propyl, (6) R⁵ is C₁-C₁₀ alkyl, (7) R⁷ is substituted aryl, and (8) each of X¹ and X² is independently chloro or methyl.

22. The catalyst compound of claim 13, wherein the catalyst compound is selected from the group consisting of: 123

124

125

126

127

128

129

130

23. A composition comprising: the catalyst compound of claim 13 represented by Formula (IIa), wherein n is 1 for Formula (IIa), and the catalyst compound of claim 13 represented by Formula (IIb), wherein m is 1 for Formula (IIb), wherein a molar ratio of the catalyst compound of Formula (IIb) to catalyst compound of Formula (IIa) is about 2:1 to about 6:1.

24. A catalyst compound represented by Formula (III): 131

wherein: M of Formula (III) is a group 3 metal, group 4 metal, or group 5 metal; T of Formula (III) is a bridging group; each of X¹ and X² of Formula (III) is independently a univalent anionic ligand, or X¹ and X² are joined to form a metallocycle ring; each of R¹, R², R³, and R⁴ of Formula (III) is independently hydrogen or substituted or unsubstituted C₁ to C₆ hydrocarbyl group and, optionally, any adjacent R¹, R², R³ and R⁴ can be joined to form a cyclic structure; R⁵ is a substituted or unsubstituted C1 to C20 hydrocarbyl group; Each of R⁶ and R⁸ is independently hydrogen or a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group; R⁷ is a substituted aryl group, an unsubstituted naphthyl group, an unsubstituted anthracenyl group, or a substituted or unsubstituted heteroaryl group; and each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ is independently hydrogen or a substituted or unsubstituted C1 to C20 hydrocarbyl group, wherein optionally R⁹ and R¹¹ combine to form a substituted or unsubstituted divalent methylene or divalent ethylene group; n is an integer of 1, 2 or 3.

25. The catalyst compound of claim 24, wherein each of R¹, R², R³, and R⁴ of Formula (III) is methyl.

26. The catalyst compound of claims 24 or 25, wherein each of R⁶, and R⁸ of Formula (III) is independently a hydrogen atom.

27. The catalyst compound of any of claims 24 to 26, wherein each of R⁵ is methyl. 132

28. The catalyst compound of any of claims 24 to 27, wherein n is 1.

29. The catalyst compound of any of claims 24 to 28, wherein R⁷ of Formula (III) is a substituted aryl group represented by the formula: , wherein each of R¹⁹, R²⁰, R²¹, R²², and R²³ is independently hydrogen, hydrocarbyl, a heteroatom, or heteroatom-containing group, where at least one of R¹⁹, R²⁰, R²¹, R²², and R²³ is not hydrogen, or one or more of R¹⁹ and R²⁰, R²⁰ and R²¹, R²¹ and R²², or R²² and R²³ are joined to form a completely saturated, partially saturated, or aromatic ring.

30. The catalyst compound of any of claims 24 to 29, wherein R⁷ of Formula (III) is selected from the group consisting of: 31. The catalyst compound of any of claims 24 to 30, wherein each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ of Formula (III) is hydrogen. 32. The catalyst compound of any of claims 24 to 31, wherein: T of Formula (III) is selected from the group consisting of Si(CH₃)₂, Si(CH₂CH₃)₂, and Si(CH2CH2CH3)2, M of Formula (III) is zirconium or hafnium, and each of X¹ and X² of Formula (III) is chloro. 33. The catalyst compound of claim 24, wherein for Formula (III): (1) M is zirconium or hafnium, (2) T is Si(CH₃)₂, Si(CH₂CH₃)₂, or Si(CH₂CH₂CH₃)₂, (3) each of R⁶ and R⁸ is independently hydrogen or unsubstituted C1-C10 alkyl, 133

(4) each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ is independently hydrogen, (5) each of R¹, R², R³, and R⁴ is independently methyl, ethyl, or propyl, (6) R⁵ is C₁-C₁₀ alkyl, (7) R⁷ is substituted aryl, (8) each of X¹ and X² is independently chloro or methyl, and (9) n is 1. 34. The catalyst compound of claim 24, wherein the catalyst compound is selected from the group consisting of: 134

135

136

137 35. A catalyst system comprising (1) an activator, (2) the catalyst compound of any of claims 12 to 22, or claims 24-34 or composition of claim 23, and (3) an optional support material. 36. A process for producing an alpha olefin homopolymer or copolymer, the process comprising: polymerizing one or more C2-C20 alpha-olefins by introducing the one or more C2-C20 alpha olefins and optionally hydrogen with the catalyst system of claim 35, in solution, gas phase, or slurry reactor, in series, or in parallel, at a reactor pressure of about 0.05 MPa to about 1,500 MPa and a reactor temperature of about 30°C to about 230°C to form the alpha olefin homopolymer or copolymer. 37. The process of claim 36, wherein the one or more C₂-C₂₀ alpha-olefins consist of propylene to form the alpha olefin homopolymer, wherein the alpha olefin homopolymer is an isotactic polypropylene. 38. The process of claim 37, wherein the isotactic polypropylene has the following properties: (1) an average meso run length of about 98 or greater, (2) an [mmmm] pentad content of about 95.0% to about 99.5%,

(3) a melting point (Tm) of about 157°C to about 159°C, and (4) a weight average molecular weight (Mw) of about 150,000 g/mol or greater. 139