WO2026024944A1 - Metallocene catalyst compounds for producing polyolefins - Google Patents

Abstract

In some embodiments, a catalyst compound represented by Formula (I). M of Formula (I) is a group 3 metal, group 4 metal, or group 5 metal. 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, unsubstituted naphthyl group, unsubstituted anthracenyl group, or substituted or unsubstituted heteroaryl group. R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently hydrogen or a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group.

Description

Title: METALLOCENE CATALYST COMPOUNDS FOR PRODUCING POLYOLEFINS INVENTORS: Alexander V. Zabula; Torin J. Dupper; Nikola S. Lambic; Lubin Luo CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of and priority to US Provisional Application No. 63/675,588 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, ethylene copolymers are polymers that have a large variety of uses. Processes for the manufacture of ethylene copolymers have evolved with improvement in catalyst technology, from complex slurry processes using an inert hydrocarbon diluent, to simpler bulk processes using liquid ethylene and comonomer 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 and particularly for forming linear low density polyethylene (LLDPE). 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, in the case of propylene-ethylene copolymers, metallocene catalysts having high activity are also known to have limited comonomer incorporation, limited molecular weight capability, and narrow polydispersity indices. For example, propylene impact copolymers are commonly used in a variety of applications where strength and impact resistance are desired, such as molded and extruded automobile parts, household appliances, luggage and furniture. Propylene homopolymers are often unsuitable for such applications because they tend to be brittle and have low impact resistance particularly at low temperature, whereas propylene impact copolymers are specifically engineered for applications such as these. A typical propylene impact copolymer contains two phases or components, a polypropylene (typically homopolypropylene) component and a propylene copolymer component. These two components are usually produced in a sequential polymerization process wherein the polypropylene produced in a first reactor is transferred to a second reactor where copolymer is produced and incorporated within the matrix of the homopolymer component. The copolymer component typically has rubbery characteristics and provides the desired impact resistance, whereas the polypropylene homopolymer provides overall stiffness. [0008] Recently, efforts have been made to prepare propylene impact copolymers using the metallocene catalysis technology in order to capitalize on the inherent benefits such catalysts are known to provide. Metallocene catalyzed homopolymers typically have narrow molecular weight distributions, low extractables, and a variety of other favorable properties associated therewith. Unfortunately, most known metallocenes are not able to provide copolymer components with high enough molecular weight and increased ethylene content (as compared to conventional PE copolymers) for better impact properties (due to decreased crystallinity/more amorphous) under commercially relevant process conditions where the metallocene catalyst has high activity. The resulting propylene impact copolymers therefore tend to have poor impact strength compared to their conventionally catalyzed counterparts. [0009] 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 ethylene-octene copolymers and/or propylene-ethylene copolymers at high molecular weight and high catalyst activity. [0010] References for citing in an Information Disclosure Statement (37 C.F.R.1.97(h)): WO2006-065906A2 - Halogen substituted metallocene compounds for olefin polymerization; 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; CN104231003 - Bridged indene fluorene zirconium, hafnium compound and preparation method and application in propylene oligomerization; Schneider, N. et al. (1997) “ansa-Zirconocene Complexes with Modified Benzindenyl Ligands: Syntheses, Crystal Structure, and Properties as Propene Polymerization Catalysts,” Organometallics, v.16(15), pp.3413-3420; Foster, P. et al. (1998) “Synthesis and Polymerization Behavior of Tetrahydro-2-Methylbenzindenyltitanium and Zirconium Compounds,” Journal of Organometallic Chemistry, v.571(2), pp.171-181; Xu, G. et al. (2000) “Syndiospecific Polymerization of Styrene with Half-Sandwich Titanocene Catalysts. Influence of Ligand Pattern on Polymerization Behavior,” Macromolecules, v.33(8), pp.2825-283. SUMMARY [0011] The present disclosure relates to ansa-metallocene catalyst compounds, catalyst systems comprising such compounds, and uses thereof. [0012] In some embodiments, a catalyst compound represented by Formula (I): where: M of Formula (I) 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, unsubstituted naphthyl group, unsubstituted anthracenyl group, or substituted or unsubstituted heteroaryl group; R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently hydrogen or a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group. [0013] In some embodiments, a catalyst compound represented by Formula (II): 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 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 hydrocarbyl group; n is an integer of 1, 2 or 3. [0014] In some embodiments, a process for producing an alpha 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. DETAILED DESCRIPTION [0015] 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. [0016] Catalyst compounds of the present disclosure can have 2-substituted 6,7,8,9- tetrahydro-cyclopenta[a]naphthalenyl moieties. Catalyst compounds of the present disclosure can have a substituted aryl moiety at the 5-position of the 6,7,8,9-tetrahydro- cyclopenta[a]naphthalenyl ring. [0017] It has been discovered that catalysts of the present disclosure can exhibit excellent activities, particularly for supported metallocene catalysts and particularly for forming linear low density polyethylene (LLDPE). [0018] In addition, in the case of propylene-ethylene copolymers, metallocene catalysts having high activity of the present disclosure can provide propylene-ethylene copolymers having high molecular weight and broad polydispersity indices. Metallocene catalysts of the present disclosure can provide copolymer components with high molecular weight, broader molecular weight distribution, and increased ethylene content (as compared to conventional PE copolymers) for better impact properties under commercially relevant process conditions where the metallocene catalyst has high activity. Broader molecular weight distribution and increased ethylene content provides controllable impact resistance to broaden the possible uses of impact copolymers. [0019] 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. [0020] 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. [0021] The terms “substituent,” “radical,” “group,” and “moiety” may be used interchangeably. [0022] 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. [0023] As used herein, “polyethylene” can include “ethylene homopolymer”, “ethylene copolymer”, or combinations thereof. “Polypropylene” can include “propylene homopolymer”, “propylene copolymer”, or combinations thereof. [0024] 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. [0025] For the purposes of the present disclosure, ethylene shall be considered an alpha- olefin. [0026] 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 “C_m-C_y” 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. [0027] 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. [0028] 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. [0029] 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. [0030] 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. [0031] 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. [0032] 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 pseudo aromatic 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. [0033] 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.

[0034] 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. [0035] 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. [0036] As used herein, the term “monocyclic arenyl ligand” is used herein to mean a substituted or unsubstituted monoanionic C₅ to C₁₀₀ hydrocarbyl ligand that contains an aromatic five-membered single hydrocarbyl ring structure (also referred to as a cyclopentadienyl ring). [0037] As used herein, the term “polycyclic arenyl ligand” is used herein to mean a substituted or unsubstituted monoanionic C₉ to C₁₀₃ 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. [0038] 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). [0039] 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. [0040] 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. [0041] 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. [0042] The terms “catalyst compound”, “catalyst complex”, “transition metal complex”, “transition metal compound”, “precatalyst compound”, and “precatalyst complex” are used interchangeably. [0043] 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. [0044] 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. [0045] 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. [0046] 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. [0047] 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 Oliveira, J. V. et al. (2000) “High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems,” Ind. Eng. Chem. Res., v.29, pp.4627-4633. [0048] 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%. [0049] 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, US Patent 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. 6,833,417; 6,841,630; 6,989,344; 7,202,313; 7,504,463; 7,563,851; 7,915,357; 8,101,691; and 8,129,484; for discussion of suitable gas phase fluidized bed polymerization systems, which are incorporated herein by reference. [0050] 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. [0051] 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. [0052] 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. [0053] 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. [0054] 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. [0055] The terms “process” and “method” are used interchangeably. Catalyst Compounds [0056] This disclosure relates to metallocene catalyst compounds represented by Formula (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 or 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 hydrocarbyl group (such as divalent ethylene or divalent methylene). [0057] In some embodiments, a catalyst compound is represented by Formula (II):

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 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 hydrocarbyl group (such as divalent methylene or divalent ethylene); n is an integer of 1, 2 or 3. [0058] In some embodiments, R¹, R², R³, and R⁴ of Formula (I) or Formula (II) 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. [0059] In some embodiments, R⁵ of Formula (I) or Formula (II) 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, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, n-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. [0060] In some embodiments, R⁶ and R⁸ of Formula (I) or Formula (II) 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. [0061] In some embodiments, R⁷ of Formula (I) or Formula (II) is a substituted aryl group represented by the formula: , wherein each of R^17’, R^{18’ 19’ 20’ 21’} , R , R , and R is independently hydrogen, hydrocarbyl, a heteroatom, or heteroatom-containing group, where at least one of R^17’, R^18’, R^19’, R^20’, or R^21’ is not hydrogen, or one or more of R^17’ and R^18’, R^18’ and R^19’, R^19’ and R^20’, or R^20’ and R^21’ are joined to form a completely saturated, partially saturated, or aromatic ring. In some embodiments, each of R^17’, R^18’, R^19’, R^20’, and R^21’ 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 R^17’, R^18’, R^19’, R^20’, or R^21’ is not hydrogen. In some embodiments, each of R^17’, R^18’, R^19’, R^20’, and R^21’ is independently hydrogen, methyl, ethyl, isopropyl, tert-butyl, C₁-C₆ alkoxyl, or phenyl, where at least one of R^17’, R^18’, R^19’, R^20’, and R^21’ is not hydrogen. In some embodiments, at least one of R^17’, R^18’, R^19’, R^20’, and R^21’ is not hydrogen and is an electron donating group. [0062] In some embodiments, R⁷ of Formula (I) or Formula (II) is selected from: . [0063] In some embodiments, R⁷ of Formula (I) or Formula (II) is selected from an unsubstituted naphthyl group or an unsubstituted anthracenyl group. [0064] In some embodiments, R⁷ of Formula (I) or Formula (II) 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. [0065] In some embodiments, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ of Formula (I) or Formula (II) are each independently hydrogen. In some embodiments, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently hydrogen or an unsubstituted C₁ to C₆ hydrocarbyl group. In some embodiments, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl. In some embodiments, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, n-pentyl, isopentyl, or neopentyl. [0066] In some embodiments, T of Formula (I) or Formula (II) 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. [0067] In some embodiments of Formula (I) or Formula (II), M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf). In some embodiments, M is Zr or Hf. [0068] In some embodiments, X¹ and X² of Formula (I) or Formula (II) 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. [0069] 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, 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. [0070] 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, (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 C₁-C₅ alkyl, (7) R⁷ is substituted aryl, and (8) each X¹ and X² is chloro. [0071] 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, (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. [0072] In some embodiments of Formula (I), the catalyst is selected from: [0073] In some embodiments of Formula (I), the catalyst is selected from: [0074] 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. [0075] 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. Methods of Preparing Catalyst Compounds [0076] 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.

Catalyst Systems [0077] 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. [0078] 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 [0079] The terms “cocatalyst” and “activator” are used herein interchangeably. [0080] 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, σ-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. [0081] In at least one embodiment, the catalyst system includes an activator, a catalyst compound of Formula (I) and optional support. [0082] In at least one embodiment, 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. Alumoxane Activators [0083] 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. [0084] 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. [0085] 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 [0086] 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. [0087] 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. [0088] 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. [0089] 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. [0090] 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). [0091] 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. [0092] 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, US 5,153,157; US 5,453,410; EP0573120 B1; WO1994-007928; and WO1995-014044, incorporated herein by reference, which discuss the use of an alumoxane in combination with an ionizing activator). [0093] 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. [0094] 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 [0095] 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. [0096] 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. [0097] In some embodiments, an activator compound is represented by Formula (AI): [R¹R²R³EH]_d ⁺[M^k+Q_n]^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. [0098] 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). [0099] 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). [0100] 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). [0101] 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 [0102] 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. [0103] 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. [0104] The support material, such as an inorganic oxide, can have a surface area of about 10 m² /g to about 700 m² /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 about 50 m² /g to about 500 m² /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 material can be about 100 m² /g to about 400 m² /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 m² /gm; pore volume of 1.65 cm³ /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). [0105] 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. [0106] 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 hour to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours at temperatures from -25°C 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. [0107] 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 hour to about 24 hours, such as about 2 hours to about 16 hours, or about 4 hours to about 8 hours. [0108] 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. [0109] 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 [0110] 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. [0111] 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. [0112] 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. [0113] 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. [0114] 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. In some embodiments, 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). [0115] 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. [0116] 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. [0117] 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. [0118] 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. [0119] 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). [0120] 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. [0121] 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. [0122] 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^-1hr^-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. [0123] In at least one embodiment, according to the present disclosure, a catalyst system used for producing ethylene homopolymers has a catalyst activity of greater than 500 kg/mmolcat^-1hr^-1, such as greater than 600 kg/mmolcat^-1hr^-1, such as greater than 700 kg/mmolcat^-1hr^-1, such as about 500 kg/mmolcat^-1hr^-1 to about 700 kg/mmolcat^-1hr^-1, such as about 500 kg/mmolcat^-1hr^-1 to about 600 kg/mmolcat^-1hr^-1, alternatively about 600 kg/mmolcat- ¹hr^-1 to about 700 kg/mmolcat^-1hr^-1. [0124] In at least one embodiment, according to the present disclosure, a catalyst system used for producing ethylene-octene copolymers has a catalyst activity of greater than 700 kg/mmolcat^-1hr^-1, such as greater than 800 kg/mmolcat^-1hr^-1, such as greater than 900 kg/mmolcat^-1hr^-1, such as about 500 kg/mmolcat^-1hr^-1 to about 900 kg/mmolcat^-1hr^-1, such as about 500 kg/mmolcat^-1hr^-1 to about 600 kg/mmolcat^-1hr^-1, alternatively about 600 kg/ mmolcat^-1hr^-1 to about 700 kg/mmolcat^-1hr^-1, alternatively about 700 kg/mmolcat^-1hr^-1 to about 800 kg/mmolcat^-1hr^-1. [0125] In at least one embodiment, according to the present disclosure, a catalyst system used for producing propylene-ethylene copolymers has a catalyst activity of greater than 800 kg/mmolcat^-1hr^-1, such as greater than 900 kg/mmolcat^-1hr^-1, such as greater than 1,000 kg/mmolcat^-1hr^-1, such as about 800 kg/mmolcat^-1hr^-1 to about 1,000 kg/mmolcat^-1hr^-1, such as about 900 kg/mmolcat^-1hr^-1 to about 1,000 kg/mmolcat^-1hr^-1, such as about 950 kg/ mmolcat^-1hr^-1 to about 1,000 kg/mmolcat^-1hr^-1. [0126] 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. [0127] 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. [0128] 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 [0129] The present disclosure also relates to compositions of matter produced by the methods described herein. [0130] 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). [0131] 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 3 wt% to about 10 wt%, such as about 4 wt% to about 9 wt%, alternatively 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 3 wt% to about 10 wt%, such as about 4 wt% to about 9 wt%, alternatively 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. [0132] In at least one embodiment, the polymers produced herein are homopolymers of propylene or are copolymers of propylene having, for example, about 30 wt% to about 55 wt% (such as about 35 wt% to about 50 wt%, such as about 40 wt% to about 50 wt%, such as about 40 wt% to about 45 wt%, alternatively about 45 wt% to about 49 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 30 wt% to about 55 wt% (such as about 35 wt% to about 50 wt%, such as about 40 wt% to about 50 wt% such as about 40 wt% to about 45 wt%, alternatively about 45 wt% to about 49 wt%, based on the weight of the polymer. [0133] 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). [0134] In at least one embodiment, a propylene homopolymer or propylene copolymer of the present disclosure has an Mw about 100,000 g/mol to about 300,000 g/mol, such as about 125,000 g/mol to about 175,000 g/mol, alternatively about 130,000 g/mol to about 160,000 g/mol, such as about 140,000 g/mol to about 145,000 g/mol, alternatively about 145,000 g/mol to about 150,000 g/mol. [0135] In at least one embodiment, a propylene homopolymer or propylene copolymer of the present disclosure has an Mn of about 10,000 g/mol to about 300,000 g/mol, such as about 10,000 g/mol to about 100,000 g/mol, such as about 10,000 g/mol to about 30,000 g/mol, such as about 10,000 g/mol to about 20,000 g/mol, such as about 15,000 g/mol to about 20,000 g/mol. [0136] In at least one embodiment, a propylene homopolymer or propylene copolymer of the present disclosure has an Mw/Mn (PDI) value about 3 to about 12, such as about 5 to about 12, such as about 7 to about 12, such as about 8 to about 9, alternatively about 9 to about 10. [0137] In at least one embodiment, an ethylene homopolymer or ethylene copolymer of the present disclosure has an Mw about 50,000 g/mol to about 1,100,000 g/mol, such as about 100,000 g/mol to about 200,000 g/mol, alternatively about 100,000 g/mol to about 125,000 g/mol, alternatively about 125,000 g/mol to about 150,000 g/mol, alternatively about 50,000 g/mol to about 100,000 g/mol, alternatively about 100,000 g/mol to about 500,000 g/mol, alternatively about 500,000 g/mol to about 850,000 g/mol. [0138] In at least one embodiment, an ethylene homopolymer or ethylene copolymer of the present disclosure has an Mn of about 1,000 g/mol to about 100,000 g/mol, such as about 5,000 g/mol to about 10,000 g/mol, alternatively about 10,000 g/mol to about 20,000 g/mol, alternatively about 20,000 g/mol to about 30,000 g/mol, alternatively about 30,000 g/mol to about 40,000 g/mol. [0139] In at least one embodiment, an ethylene homopolymer or ethylene copolymer of the present disclosure has an Mw/Mn (PDI) value about 2 to about 15, such as about 5 to about 12, such as about 5 to about 9, alternatively about 9 to about 12, alternatively about 12 to about 15. GPC 4-D [0140] 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: where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, α_PS = 0.67 and K_PS = 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, α = 0.705 and K = 0.0000229 for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, α = 0.695 and K = 0.000579 for linear ethylene polymers, α = 0.705 and K = 0.0002288 for linear propylene polymers, and α = 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. [0141] 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 f is 0.3, 0.4, 0.6, 0.8, and so on for C₃, C₄, C₆, C₈, and so on co-monomers, respectively: w2 = f ∗ SCB/1000TC . [0142] 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 . [0143] 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 w2b = f ∗ bulk CH3/1000TC bulk SCB/1000TC = bulk CH3/1000TC - bulk CH3end/1000TC and bulk SCB/1000TC is converted to bulk w2 in the same manner as described above. [0144] 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.): [0145] Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, 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 NA 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. [0146] 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 a ] , where αps is 0.67 and K_ps is 0.000175. [0147] 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 α are for the reference linear polymer, which are, for purposes of this present disclosure and claims thereto, α = 0.705 and K = 0.0000229 for ethylene- propylene copolymers and ethylene-propylene-diene terpolymers, α = 0.695 and K = 0.000579 for linear ethylene polymers, α = 0.705 and K = 0.0002288 for linear propylene polymers, α = 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 [0148] 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. [0149] 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 wt% to about 90 wt%. [0150] 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 [0151] 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. [0152] 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 [0153] The experimental methods and analytical techniques utilized in Examples below are described in this section. [0154] Olefin polymerization catalyst with unsubstituted 6,7,8,9-tetrahydro- cyclopenta[a]naphthalenyl core is shown as comparative C1. [0155] Here, C1-symmetric catalysts I1-I7 with the aryl substituted 6,7,8,9-tetrahydro- cyclopenta[a]naphthalenyl fragment (Scheme 2) for olefin polymerization have been prepared using a high-yield multi-step synthesis described in the experimental section (Scheme 1 above) and demonstrated beneficial catalytical properties compared to C1. The activities for newly prepared systems I1-I7 were studied for ethylene homopolymerization, ethylene/1-octene copolymerization, ethylene/propylene copolymerization and propylene homopolymerization in high-throughput PPR and 1L or 2L reactors.

Scheme 2. Novel I1-I7 and comparative C1-C8 catalysts. [0156] The activity of the catalysts I1-I7 for ethylene and ethylene/1-octene polymerization are summarized in Table 1. The activity of new Zr-based catalysts remains similar to unsubstituted C1 but noticeably higher than that observed for C2, C6, C7 and C8 (S-cat). For ethylene/1-octene copolymerization, the activity for invented systems I1, I2 and I5 is substantially higher (up to 860 kg/mmolcat hr) compared to C1 (719 kg/mmolcat hr). Thus, there is a clear advantage to use the invented systems as good LAO incorporators for the production of LLDPE. Table 1. Ethylene homopolymerization and ethylene/1-octene copolymerization data for I1-I7, C1, C2, C6, C7 and C8 (PPR, 0.02 μmol catalyst, MAO/catalyst ratio 500, isohexane, 115 psi ethylene, 85°C). Each value is an average of 2 runs. [0157] Ethylene homopolymerization for supported on silica catalysts I1 and I2 gave the activity similar to C7 and C8 (Table 2). The invented catalysts show a good response to H₂ and produce branched PE products (g’ 0.75-0.93). Table 2. Ethylene polymerization data for supported I1, I2, C2-C4, C6 and C7 in 1L reactor. Conditions: isobutane, 85°C, 30 minutes, scavenger – 1M TIBAL) Table 2. Continued [0158] The catalysts I1 and I2 exhibit slightly higher activity for propylene homopolymerization compared to C1 but much lower compared to other comparative examples (Table 3). The Mw’s of PP produced by I1 and I2 is ca 3 times lower than the PP products obtained from C2-C6). Table 3. Polypropylene polymerization data for I1 and I2 and C1-C6 (1 g propylene, 0.03 μmol catalyst, MAO/catalyst ratio 500, 70°C). Each value is an average of 3 runs. [0159] In order to illustrate the performance of new catalysts in slurry propylene polymerization – inventive catalysts I1 and I2 and comparative examples C2-C4, C6 and C7 were supported using silica supported MAO (sMAO) and tested under industrially relevant propylene polymerization conditions at 70°C (Table 4). The polymer products, generated using new catalysts, demonstrate low Mw capability and low Tm (148°C). Therefore, due to the high MFR, the resulting polypropylene are more suitable for making fiber filaments in spunbond and meltblow processes compared to the polypropylene derived from the comparative examples. Table 4. Propylene polymerization data for I1, I2, C2-C4, C6 and C7 in 2L reactor. [0160] For ethylene/propylene copolymerization the catalysts I1 and I2 demonstrate higher activity than comparative systems C1 or C5 and much broader polydispersity (Table 5). Moreover, I1 and I2 incorporate higher amounts of ethylene vs comparative examples. Table 5. Ethylene/propylene polymerization data for I1 and I2 and C1-C6 (0.02 μmol catalyst, MAO/catalyst ratio 500, 70°C). Each value is an average of 3 runs. 5-Bromo-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalene [0161] 5-Bromo-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalene was prepared according to the literature (WO2006-065906A2). 5-(3,5-di-tert-Butyl-4-methoxyphenyl)-2-methyl-6,7,8,9-tetrahydro-3H- cyclopenta[a]naphthalene [0162] 5-Bromo-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalene (0.90 g, 3.42 mmol), (3,5-di-tert-butyl-4-methoxyphenyl)boronic acid (1.24 g, 3.59 mmol), K₂CO₃ (1.04 g, 7.52 mmol), bis(dibenzylideneacetone)palladium(0) (197 mg, 0.342 mmol), 1,3,5,7- tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (130 mg, 0.445 mmol) and THF (30 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 × 50 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 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. Evaporation of solvents afforded a product as a yellow solid. Yield: 1.31 g (95%). ¹H NMR (400 MHz, CDCl₃): δ 7.22 (s, 2H), 7.08 (s, 1H), 6.51 (s, 1H), 3.78 (s, 3H), 3.21 (s, 2H), 2.83 (t, J = 6.5 Hz, 2H), 2.67 (t, J = 6.2 Hz, 2H), 2.21 (s, 3H), 1.94 – 1.85 (m, 2H), 1.80 – 1.71 (m, 2H), 1.49 (s, 18H). 5-(4-(tert-Butyl)phenyl)-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalene [0163] 5-Bromo-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalene (0.90 g, 3.42 mmol), (4-(tert-butyl)phenyl)boronic acid (0.64 g, 1.90 mmol), K₂CO₃ (1.04 g, 7.52 mmol), bis(dibenzylideneacetone)palladium(0) (197 mg, 0.342 mmol), 1,3,5,7-tetramethyl-6-phenyl- 2,4,8-trioxa-6-phosphaadamantane (130 mg, 0.445 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 16 hours. Then, the flask was cooled to the ambient temperature and the reaction volume was reduced to ca 5 mL. Water (50 mL) was added and the product was extracted into Et₂O/EtOAc (1:1, 3 × 50 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 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. Further purification was achieved upon recrystallization from MeOH as a light orange powder. Yield: 0.88 g (81%). ¹H NMR (500 MHz, CDCl₃): δ 7.43 (d, J = 8.4 Hz, 2H), 7.28 (d, J = 8.4 Hz, 2H), 7.04 (s, 1H), 6.48 (h, J = 1.6 Hz, 1H), 3.20 (m, 2H), 2.82 (t, J = 6.5 Hz, 2H), 2.67 (t, J = 6.3 Hz, 2H), 2.19 (d, J = 1.4 Hz, 3H), 1.89-1.87 (m, 2H), 1.75–1.73 (m, 2H), 1.40 (s, 9H).¹³C NMR (126 MHz, CDCl₃): δ 149.16, 145.15, 142.69, 140.84, 140.51, 139.83, 131.97, 130.25, 129.05, 127.00, 124.75, 119.15, 41.43, 34.50, 31.46, 28.61, 27.08, 23.70, 22.89, 16.84. 5-([1,1'-Biphenyl]-2-yl)-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalene [0164] 5-Bromo-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalene (0.90 g, 3.42 mmol), [1,1'-biphenyl]-2-ylboronic acid (0.71 g, 3.59 mmol), K₂CO₃ (1.04 g, 7.52 mmol), bis(dibenzylideneacetone)palladium(0) (197 mg, 0.342 mmol), 1,3,5,7-tetramethyl-6-phenyl- 2,4,8-trioxa-6-phosphaadamantane (130 mg, 0.445 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 16 hours. Then, the flask was cooled to the ambient temperature and the reaction volume was reduced to ca 5 mL. Water (50 mL) was added, and the product was extracted into Et₂O/EtOAc (1:1, 3 × 50 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 green oil. The product was dissolved in the CH₂Cl₂/n-hexane mixture (1:4, v:v, respectively) and passed through a short silica gel plug. Further purification was achieved boiling in n-pentane to give a light-yellow solid. Yield: 0.85 g (74%). ¹H NMR (500 MHz, CDCl₃): δ 7.49 – 7.43 (m, 2H), 7.40 (td, J = 7.3, 1.8 Hz, 1H), 7.33 (dd, J = 7.3, 1.6 Hz, 1H), 7.25 – 7.14 (m, 5H), 6.98 (s, 1H), 6.45 (h, J = 1.7 Hz, 1H), 3.15 (s, 2H), 2.67 (q, J = 6.3, 5.8 Hz, 2H), 2.40-2.35 (m, 1H), 2.18 (s, 3H), 2.15-2.09 (m, 1H), 1.80 – 1.71 (m, 1H), 1.65 – 1.57 (m, 2H), 1.52 – 1.43 (m, 1H).¹³C NMR (126 MHz, CDCl₃): δ 144.74, 142.23, 141.68, 141.25, 140.97, 140.65, 139.55, 131.60, 131.05, 130.47, 129.87, 129.33, 127.63, 127.23, 127.16, 126.96, 126.24, 119.76, 41.35, 27.96, 26.84, 23.32, 22.84, 16.84. 5-(3,5-di-tert-Butylphenyl)-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalene [0165] 5-Bromo-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalene (0.90 g, 3.42 mmol), (3,5-di-tert-butylphenyl)boronic acid (0.841 g, 3.59 mmol), K₂CO₃ (1.04 g, 7.52 mmol), bis(dibenzylideneacetone)palladium(0) (197 mg, 0.342 mmol), 1,3,5,7-tetramethyl-6-phenyl- 2,4,8-trioxa-6-phosphaadamantane (130 mg, 0.445 mmol) and THF (30 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 16 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 × 50 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 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. Evaporation of solvents afforded a product which 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. Yield: 0.89 g (70%). ¹H NMR (500 MHz, CDCl₃): δ 7.42 (t, J = 1.9 Hz, 1H), 7.22 (d, J = 1.9 Hz, 2H), 7.11 (s, 1H), 6.53 (h, J = 1.6 Hz, 1H), 3.23 (s, 2H), 2.85 (t, J = 6.5 Hz, 2H), 2.68 (t, J = 6.3 Hz, 2H), 2.22 (d, J = 1.5 Hz, 3H), 1.94 – 1.86 (m, 2H), 1.80-1.74 (m, 2H), 1.40 (s, 18H). ¹³C NMR (126 MHz, CDCl₃): δ 150.07, 145.20, 142.75, 141.81, 141.73, 140.87, 132.09, 130.21, 127.03, 123.82, 120.14, 119.12, 41.46, 34.92, 31.60, 28.63, 27.15, 23.77, 22.89, 16.89. 9-(2-Methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalen-5-yl)anthracene [0166] 5-Bromo-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalene (1.50 g, 5.70 mmol), anthracen-9-ylboronic acid (1.33 g, 5.98 mmol), K₂CO₃ (1.73 g, 12.5 mmol), bis(dibenzylideneacetone)palladium(0) (328 mg, 0.57 mmol), 1,3,5,7-tetramethyl-6-phenyl- 2,4,8-trioxa-6-phosphaadamantane (217 mg, 0.741 mmol) and THF (30 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 3 days. 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 × 50 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 brown oil. The product was dissolved in the CH₂Cl₂/n-hexane mixture (1:4, v:v, respectively) and passed through a short silica gel plug. Evaporation of solvents afforded a product which was further purified on Biotage automated column using silica gel and the mixture of ethyl acetate and n-hexane (1:9, v:v, respectively) as an eluent. Yield: 1.20 g (58%). ¹H NMR (400 MHz, CDCl₃): δ 8.51 (s, 1H), 8.08 (d, J = 8.5 Hz, 2H), 7.64 (d, J = 8.8 Hz, 2H), 7.48 (ddd, J = 8.3, 6.5, 1.2 Hz, 2H), 7.35 (ddd, J = 8.8, 6.6, 1.4 Hz, 2H), 7.08 (s, 1H), 6.54 (h, J = 1.5 Hz, 1H), 3.35 (s, 2H), 2.92 (t, J = 6.5 Hz, 2H), 2.26 (d, J = 1.5 Hz, 3H), 2.15 (t, J = 6.4 Hz, 2H), 1.89-1.83 (m, 2H), 1.65–1.57 (m, 2H). ¹³C NMR (101 MHz, CDCl₃): δ 145.22, 142.73, 141.34, 137.70, 136.25, 132.19, 132.16, 131.54, 130.18, 128.41, 127.24, 126.92, 125.93, 125.20, 125.07, 120.38, 41.56, 27.20, 23.49, 22.96, 16.91. (5-(3,5-di-tert-Butyl-4-methoxyphenyl)-2-methyl-6,7,8,9-tetrahydro- cyclopenta[a]naphthalenyl)lithium [0167] nBuLi (1.14 mL, 1.60 M in hexane, 1.83 mmol) was added dropwise to a precooled solution (-35°C) of 5-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-6,7,8,9-tetrahydro-3H- cyclopenta[a]naphthalene (0.70 g, 1.74 mmol) in Et₂O (30 mL). The resulting mixture was gradually warmed to the ambient temperature. The volatiles were evaporated, and the resulting solid product was suspended in n-hexane (10 mL) and collected via filtration. The filtration cake was washed with n-hexane (3 × 5 mL) and dried in vacuo. Yield: 0.709 g, 97%. ¹H NMR (400 MHz, THF-d₈): δ 7.21 (s, 2H), 7.01 (s, 1H), 5.76 (s, 1H), 5.71 (s, 1H), 3.74 (s, 3H), 2.96 (t, J = 6.5 Hz, 2H), 2.66 (t, J = 6.2 Hz, 2H), 2.38 (s, 3H), 1.93-1.87 (m, 2H), 1.83–1.66 (m, 2H), 1.49 (s, 18H).¹³C NMR (101 MHz, THF-d₈): δ 157.57, 142.13, 141.40, 130.19, 128.93, 128.50, 126.93, 126.50, 124.66, 119.42, 119.04, 93.45, 90.39, 64.50, 36.29, 32.79, 32.53, 30.26, 28.51, 16.59, 15.69. (5-(4-(tert-Butyl)phenyl)-2-methyl-6,7,8,9-tetrahydro-cyclopenta[a]naphthalenyl)lithium [0168] nBuLi (1.30 mL, 2.70 M in hexane, 3.51 mmol) was added dropwise to a precooled solution (-35°C) of 5-(4-(tert-butyl)phenyl)-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalene (1.10 g, 3.48 mmol) in Et₂O (30 mL). The resulting mixture was gradually warmed to the ambient temperature. The volatiles were evaporated, and the resulting oil product was suspended in n-pentane (10 mL). The formed white solid was collected by filtration and washed with n-pentane (2 × 5 mL) and dried in vacuo. Yield: 1.00 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), 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). 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, 33.94, 30.99, 29.19, 27.53, 25.02, 15.62, 14.73. (5-([1,1'-Biphenyl]-2-yl)-2-methyl-6,7,8,9-tetrahydro-cyclopenta[a]naphthalenyl)lithium [0169] nBuLi (2.37 mL, 1.60 M in hexane, 3.79 mmol) was added dropwise to a precooled solution (-35°C) of 5-([1,1'-biphenyl]-2-yl)-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalene (0.85 g, 2.53 mmol) in Et₂O (20 mL). The resulting mixture was gradually warmed to the ambient temperature before adding n-pentane (10 mL). The formed white solid was collected by filtration and washed with n-pentane (2 × 5 mL) and dried in vacuo. Yield: 0.686 g, 79%. ¹H NMR (400 MHz, THF-d₈): δ 7.45–7.33 (m, 1H), 7.33–7.19 (m, 5H), 7.15–6.97 (m, 3H), 6.95 (s, 1H), 5.67 (s, 1H), 5.64 (s, 1H), 2.83 (m, 2H), 2.36 (s, 3H), 2.34-2.32 (m, 1H), 2.26– 2.08 (m, 1H), 1.75–1.43 (m, 4H). ¹³C NMR (101 MHz, THF-d₈): δ 144.54, 143.02, 141.15, 131.84, 129.29, 129.25, 127.89, 127.53, 127.02, 125.92, 125.56, 125.35, 125.23, 125.11, 123.73, 118.90, 118.64, 92.65, 89.49, 28.30, 27.30, 24.61, 15.55, 14.73. (5-(3,5-di-tert-Butylphenyl)-2-methyl-6,7,8,9-tetrahydro-cyclopenta[a]naphthalenyl)lithium [0170] nBuLi (1.37 mL, 1.60 M in hexane, 2.18 mmol) was added dropwise to a precooled solution (-35°C) of 5-(3,5-di-tert-butylphenyl)-2-methyl-6,7,8,9-tetrahydro-3H- cyclopenta[a]naphthalene (0.74 g, 1.99 mmol) in Et₂O (20 mL). The resulting mixture was gradually warmed to the ambient temperature. The volatiles were then evaporated, n-pentane added (10 mL), a formed solid product was collected by filtration, washed with n-pentane (2 × 5 mL) and dried in vacuo. Yield: 0.540 g, 72%. ¹H NMR (400 MHz, THF-d₈): δ 7.29 (t, J = 1.9 Hz, 1H), 7.19 (d, J = 1.9 Hz, 2H), 7.04 (s, 1H), 5.77 (d, J = 2.0 Hz, 1H), 5.72 (d, J = 2.0 Hz, 1H), 2.97 (t, J = 6.5 Hz, 2H), 2.66 (t, J = 6.1 Hz, 2H), 2.39 (s, 3H), 1.98–1.85 (m, 2H), 1.75-1.71 (m, 2H), 1.39 (s, 18H). ¹³C NMR (101 MHz, THF-d₈): δ 149.62, 146.32, 130.80, 128.47, 126.87, 126.50, 125.03, 124.72, 119.41, 119.11, 118.79, 93.44, 90.44, 35.36, 32.07, 31.90, 30.21, 28.52, 26.08, 16.58. (5-(Anthracen-9-yl)-2-methyl-6,7,8,9-tetrahydro-cyclopenta[a]naphthalenyl)lithium [0171] nBuLi (0.954 mL, 1.60 M in hexane, 1.53 mmol) was added dropwise to a precooled solution (-35°C) of 9-(2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalen-5-yl)anthracene (0.50 g, 1.39 mmol) in Et₂O (20 mL). The resulting mixture was gradually warmed to the ambient temperature. The volatiles were then evaporated, n-pentane added (10 mL), a formed solid product was collected by filtration, washed with n-pentane (2 × 5 mL) and dried in vacuo. Yield: 0.412 g, 81%. ¹H NMR (400 MHz, THF-d₈): δ 8.39 (s, 1H), 8.01 (d, J = 8.5 Hz, 2H), 7.93 (d, J = 8.6 Hz, 2H), 7.45–7.34 (m, 2H), 7.36–7.16 (m, 2H), 7.03 (s, 1H), 5.79 (s, 1H), 5.72 (s, 1H), 3.08 (t, J = 6.5 Hz, 2H), 2.42 (s, 3H), 2.11 (t, J = 6.2 Hz, 2H), 1.97–1.79 (m, 2H), 1.68– 1.48 (m, 2H).¹³C NMR (101 MHz, THF-d₈): δ 142.22, 131.81, 131.51, 128.52, 127.93, 127.77, 125.86, 125.73, 124.35, 124.01, 123.58, 123.04, 119.94, 119.27, 92.42, 90.12, 27.52, 24.08, 15.65. (5-(3,5-di-tert-Butyl-4-methoxyphenyl)-2-methyl-6,7,8,9-tetrahydro-3H- cyclopenta[a]naphthalen 3-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane [0172] A solution of (5-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-6,7,8,9-tetrahydro- cyclopenta[a]naphthalenyl)lithium (0.783 g, 1.91 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 (0.527 g, 1.61 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 (40 mL) 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: 0.785 g (84%). ¹H NMR (400 MHz, CDCl₃): δ 7.20 (s, 2H), 7.17 (s, 1H), 6.69 (s, 1H), 3.78 (s, 3H), 3.64 (s, 1H), 3.26 (s, 1H), 3.13–2.84 (m, 2H), 2.85–2.57 (m, 2H), 2.30 (s, 3H), 2.04 (s, 3H), 2.00 (s, 3H), 1.99 – 1.86 (m, 2H), 1.85 (s, 3H), 1.83 (s, 3H), 1.77 (m, 2H), 1.48 (s, 18H), -0.18 (s, 3H), -0.22 (s, 3H).¹³C NMR (101 MHz, CDCl₃): δ 157.80, 147.18, 143.03, 142.48, 141.88, 137.48, 137.18, 136.57, 132.99, 131.11, 128.08, 127.92, 124.24, 122.55, 64.14, 47.38, 35.80, 32.26, 27.06, 23.73, 23.05, 18.16, 14.89, 14.74, 11.23, 11.18, -4.98, -5.46. (5-(4-(tert-Butyl)phenyl)-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalen-3- yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane [0173] A solution of (5-(4-(tert-butyl)phenyl)-2-methyl-6,7,8,9-tetrahydro- cyclopenta[a]naphthalenyl)lithium (0.488 g, 1.48 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 (0.480 g, 1.46 mmol) in diethyl ether (10 mL) at -35°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 (40 mL) and filtered through a short celite plug. Concentration under a stream of nitrogen and drying in vacuo afforded the product as a white 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), 1.91 (dd, J = 12.5, 6.2 Hz, 2H), 1.84 (m, 6H), 1.75 (p, J = 5.9 Hz, 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, 136.64, 136.56, 132.99, 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. (5-([1,1'-Biphenyl]-2-yl)-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalen-3- yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane [0174] A solution of (5-([1,1'-biphenyl]-2-yl)-2-methyl-6,7,8,9-tetrahydro- cyclopenta[a]naphthalenyl)lithium (0.686 g, 2.00 mmol) in diethyl ether (10 mL) was added dropwise to a stirring solution of dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate (0.651 g, 1.98 mmol) in diethyl ether (10 mL) at -35°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 (40 mL) and filtered through a short celite plug. Concentration under a stream of nitrogen and drying in vacuo afforded the product as a white solid. Yield: 0.500 g (48%). ¹H NMR (400 MHz, CDCl₃): δ 7.55–7.26 (m, 4H), 7.23–7.10 (m, 5H), 7.05 (s, 1H), 6.66 (s, 1H), 3.63 (s, 1H), 3.20 (s, 1H), 2.95–2.85 (m, 2H), 2.49 (m, 1H), 2.27 (s, 3H), 2.23-2.19 (m, 1H), 2.04 (s, 3H), 1.98 (s, 3H), 1.85 (s, 6H), 1.82–1.55 (m, 4H), -0.39 (s, 3H), -0.58 (s, 3H). ¹³C NMR (101 MHz, CDCl₃): δ 147.05, 143.09, 141.67, 141.62, 141.41, 140.91, 136.67, 136.60, 136.23, 131.65, 131.03, 129.91, 129.36, 129.26, 128.01, 127.66, 127.60, 127.08, 126.84, 126.24, 124.35, 122.64, 47.33, 28.18, 26.81, 23.30, 23.03, 18.23, 18.09, 14.92, 14.88, 11.22, 11.18, -6.33, -6.54. (5-(3,5-di-tert-Butylphenyl)-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalen-3- yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane [0175] A solution of (5-(3,5-di-tert-butylphenyl)-2-methyl-6,7,8,9-tetrahydro- cyclopenta[a]naphthalenyl)lithium (0.540 g, 1.38 mmol) in diethyl ether (10 mL) was added dropwise to a stirring solution of dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate (0.450 g, 1.37 mmol) in diethyl ether (10 mL) at -35°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 (40 mL) and filtered through a short celite plug. Concentration under a stream of nitrogen and drying in vacuo afforded the product as a white solid. Yield: 0.76 g (99%). ¹H NMR (400 MHz, CDCl₃): δ 7.42 (t, J = 1.9 Hz, 1H), 7.23 (d, J = 1.9 Hz, 2H), 7.22 (s, 1H), 6.73 (s, 1H), 3.67 (s, 1H), 3.27 (s, 1H), 3.00 (qt, J = 17.1, 6.5 Hz, 2H), 2.80 – 2.55 (m, 2H), 2.33 (s, 3H), 2.06 (s, 3H), 2.04 (s, 3H), 1.93 (dt, J = 11.1, 6.5 Hz, 2H), 1.87 (s, 3H), 1.86 (s, 3H), 1.85 – 1.71 (m, 2H), 1.42 (m, 18H), -0.14 (s, 3H), -0.18 (s, 3H). ¹³C NMR (101 MHz, CDCl₃): δ 150.00, 149.89, 147.26, 143.14, 142.27, 141.96, 137.98, 136.55, 131.06, 128.13, 124.25, 124.02, 122.53, 119.94, 47.43, 34.91, 31.62, 28.65, 27.10, 23.71, 23.09, 22.38, 18.19, 14.91, 14.76, 11.23, 11.19, -4.85, -5.31. (5-(anthracen-9-yl)-2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalen-3- yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane [0176] A solution of (5-(anthracen-9-yl)-2-methyl-6,7,8,9-tetrahydro- cyclopenta[a]naphthalenyl)lithium (0.412 g, 1.13 mmol) in diethyl ether (10 mL) was added dropwise to a stirring solution of dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate (0.348 g, 1.11 mmol) in diethyl ether (10 mL) at -35°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 (40 mL) 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: 0.596 g (98%). ¹H NMR (400 MHz, CDCl₃): δ 8.51 (s, 1H), 8.17–8.00 (m, 2H), 7.81–7.58 (m, 2H), 7.48 (m, 2H), 7.37 (m, 2H), 7.21 (s, 1H), 6.86 (s, 1H), 3.77 (s, 1H), 3.19 (s, 1H), 3.16 – 2.91 (m, 2H), 2.37 (s, 3H), 2.31–2.04 (m, 4H), 2.00 (s, 3H), 1.98 (s, 3H), 1.92-1.85 (m, 2H), 1.81 (s, 3H), 1.76 (s, 3H), -0.15 (s, 3H), -0.25 (s, 3H). ¹³C NMR (101 MHz, CDCl₃): δ 147.38, 143.57, 142.03, 138.06, 136.60, 136.48, 133.05, 132.54, 131.65, 131.47, 130.61, 130.19, 128.43, 128.40, 128.38, 127.04, 126.81, 125.82, 125.12, 125.05, 125.02, 124.35, 123.43, 47.69, 27.20, 27.12, 23.37, 23.12, 18.13, 14.84, 11.19, 11.07, -5.28, -5.39. Synthesis of Catalyst I1. [0177] nBuLi (1.00 mL, 2.7 M in hexane, 2.7 mmol) was added dropwise to a precooled solution (-30°C) of [5-(3,5-ditert-butyl-4-methoxy-phenyl)-2-methyl-6,7,8,9-tetrahydro-3H- cyclopenta[a]naphthalen-3-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (764 mg, 1.32 mmol) in Et₂O (15 mL). The mixture was allowed to warm up to the ambient temperature under stirring over 1 hour. The resulting solution was cooled back to -30°C before solid ZrCl₄ (310 mg, 1.33 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 CH₂Cl₂ (15 mL). Filtration through a celite plug and evaporation of the solvent gave a yellow product which was suspended in n-hexane (20 mL) and stirred for 30 minutes. The yellow solid product was collected by filtration and washed by n-hexane. Drying in vacuo afforded 389 mg of the product. Yield: 40%. ¹H NMR (400 MHz, CDCl₃) δ 7.24 (s, 1H), 7.04 (s, 2H), 6.85 (s, 1H), 3.74 (s, 3H), 2.87 (m, 2H), 2.55- 2.41 (m, 2H), 2.32 (s, 3H), 2.07 (s, 3H), 2.00 (s, 3H), 1.98 (s, 3H), 1.93 (s, 3H), 1.84-1.66 (m, 4H), 1.44 (s, 18H), 1.13 (s, 3H), 1.09 (s, 3H).¹³C NMR (101 MHz, CDCl₃) δ 158.25, 142.80, 141.66, 137.40, 136.14, 134.55, 134.18, 134.14, 133.85, 132.83, 127.46, 127.32, 126.78, 123.96, 122.54, 117.95, 93.87, 83.16, 64.21, 35.80, 32.20, 28.92, 27.40, 23.49, 22.36, 18.27, 16.09, 15.55, 12.47, 12.15, 3.17, 3.14. Synthesis of Catalyst I2. [0178] nBuLi (0.98 mL, 2.7 M in hexane, 2.65 mmol) was added dropwise to a precooled solution (-30°C) of [5-(4-tert-butylphenyl)-2-methyl-6,7,8,9-tetrahydro-3H- cyclopenta[a]naphthalen-3-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (640 mg, 1.29 mmol) in Et₂O (15 mL). The mixture was allowed to warm up to the ambient temperature under stirring over 1 hour. The resulting solution was cooled back to -30°C before solid ZrCl₄ (310 mg, 1.33 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. After additional stirring for 1 hour, volatiles were evaporated, and the product was extracted into CH₂Cl₂ (15 mL). Filtration through a celite plug and evaporation of the solvent gave a yellow oil which was suspended in n-hexane (20 mL) and stirred for 30 minutes. The precipitated grey residue was removed by filtration and the hexane filtrate was concentrated to ca 5 mL and placed in the freezer at -35°C. Yellow crystalline solid was collected in 16 hours and dried in vacuo. Yield: 242 mg, 29%. ¹H NMR (400 MHz, CDCl₃) δ 7.37 (d, JHH = 8.36 Hz, 2H), 7.21 (s, 1H), 7.09 (d, JHH = 8.36 Hz), 6.85 (s, 1H), 2.92-2.81 (m, 2H), 2.50-2.42 (m, 2H), 2.31 (s, 3H), 2.06 (s, 3H), 1.99 (s, 3H), 1.92 (s, 3H), 1.91 (s, 3H), 1.84- 1.70 (m, 4H), 1.36 (s, 9H), 1.10 (s, 3H), 1.07 (s, 3H).¹³C NMR (101 MHz, CDCl₃) δ 149.51, 141.06, 139.14, 137.45, 134.55, 134.15, 134.10, 134.06, 132.73, 128.63, 127.51, 127.01, 124.84, 123.83, 122.54, 117.90, 93.97, 83.30, 34.56, 31.47, 28.86, 27.39, 23.37, 22.34, 18.29, 16.18, 15.58, 12.52, 12.17, 3.16. Synthesis of Catalyst I3. [0179] nBuLi (1.29 mL, 1.6 M in hexane, 2.07 mmol) was added dropwise to a precooled solution (-30°C) of [5-(4-tert-butylphenyl)-2-methyl-6,7,8,9-tetrahydro-3H- cyclopenta[a]naphthalen-3-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (500 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 solution was cooled back to -30°C before solid HfCl₄ (327 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 ambient temperature. After additional stirring for 1 hour, volatiles were evaporated, and the product was extracted into CH₂Cl₂ (15 mL). Filtration through a celite plug and evaporation of the solvent gave a crude product which was recrystallized from in n-pentane (15 mL) at -35°C to yield 170 mg of yellow crystals. The mother solution was concentrated to 5 mL further affording 140 mg of crystals upon cooling to -35°C. Yield: 310 mg, 41%. ¹H NMR (400 MHz, CDCl₃): δ 7.41 (d, J = 8.4 Hz, 2H), 7.28 (s, 1H), 7.15 (d, J = 8.3 Hz, 2H), 6.78 (s, 1H), 2.88 (q, J = 6.1, 5.6 Hz, 2H), 2.65–2.47 (m, 2H), 2.44 (s, 3H), 2.20 (s, 3H), 2.05 (s, 3H), 2.04 (s, 3H), 1.98 (s, 3H), 1.99–1.68 (m, 4H), 1.41 (s, 9H), 1.13 (s, 3H), 1.11 (s, 3H).¹³C NMR (101 MHz, CDCl₃): δ 149.45, 140.67, 139.18, 136.12, 133.86, 133.64, 132.88, 132.36, 132.02, 128.65, 124.82, 124.55, 123.45, 122.54, 122.16, 115.96, 96.04, 84.27, 34.54, 31.45, 28.78, 27.39, 23.41, 22.33, 18.16, 15.89, 15.30, 12.33, 11.98, 3.12, 3.10. Synthesis of Catalyst I4. [0180] nBuLi (1.24 mL, 1.6 M in hexane, 1.99 mmol) was added dropwise to a precooled solution (-30°C) of (5-([1,1'-biphenyl]-2-yl)-2-methyl-6,7,8,9-tetrahydro-3H- cyclopenta[a]naphthalen-3-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (500 mg, 0.971 mmol) in Et₂O (15 mL). The mixture was allowed to warm up to the ambient temperature under stirring over 1 hour. Then, the volatiles were evaporated, and the obtained residue was suspended in n-pentane (5 mL), collected by filtration and washed with additional portion of n-pentane to afford a beige solid. This intermediate solid product was dissolved in Et₂O (9 mL) and THF (1 mL) and cooled to -30°C. Solid ZrCl₄ (229 mg, 0.981 mmol) was added to the resulting solution 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. After additional stirring for 1 hour, volatiles were evaporated, and the product was extracted into CH₂Cl₂ (15 mL). Filtration through a celite plug and evaporation of the solvent gave a crude product which was suspended in n-hexane (20 mL), filtered, washed with n-hexane (5 mL) and dried in vacuo to afford a bright yellow mixture of two isomers (ca 4:1). Yield: 175 mg, 17%. ¹H NMR (400 MHz, CDCl₃, resonance signals for the minor isomer are shown in square brakets): δ 7.58–7.04 (m, 10H), 6.85 [6.87] (s, 1H), 2.89-2.74 (m, 2H), 2.35 [2.30] (s, 3H), 2.10 [2.09] (s, 3H), 2.04 [2.03] (s, 3H), 2.00 (s, 3H), 1.95 (s, 3H), 1.91 – 1.33 (m, 6H), 1.22 [1.03] (s, 3H), 1.09 [1.02] (s, 3H).¹³C NMR (101 MHz, CDCl₃, resonance signal for the minor isomer is shown in square brakets): δ [141.50], 141.35, [141.07], [140.84], 140.65, 140.41, 140.12, [139.82], [139.69], 137.87, 137.29, [135.35], 134.61, 134.24, [134.13], [134.00], 133.96, 133.73, 132.61, [132.20], 130.61, 129.94, 129.38, [129.28], 129.08, [129.05], 128.27, [128.01], 127.80, [127.66], 127.47, 127.27, 127.15, 127.03, [126.72], [126.61], 126.48, 125.35, [124.19], 123.57, 118.14, [94.79], 93.86, [84.96], 82.95, [28.88], 28.25, [27.32], 27.18, [23.33], 23.09, [22.44], 22.24, 21.52, [18.53], 18.23, 16.10, 15.58, [13.98], 12.55, 12.47, [12.20], 12.08, 3.14, [2.95]. Synthesis of Catalyst I5. [0181] nBuLi (0.84 mL, 1.6 M in hexane, 1.34 mmol) was added dropwise to a precooled solution (-30°C) of [5-(3,5-ditert-butyl-phenyl)-2-methyl-6,7,8,9-tetrahydro-3H- cyclopenta[a]naphthalen-3-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (360 mg, 0.653 mmol) in Et₂O (15 mL). The mixture was allowed to warm up to the ambient temperature under stirring over 1 hour. Then, the volatiles were evaporated, and the obtained residue was suspended in n-pentane (5 mL), collected by filtration and washed with additional portion of n-pentane to afford a beige solid. This intermediate solid product was dissolved in Et₂O (9 mL) and THF (1 mL) and cooled to -30°C. Solid ZrCl₄ (154 mg, 0.66 mmol) was added to the resulting solution in small portions over 10 minutes. The mixture was allowed to warm up to the ambient temperature under stirring over 1 hour. Additional stirring for 12 hours gave a yellow precipitate. Volatiles were then evaporated, and the product was extracted into CH₂Cl₂ (5 mL). Filtration through a celite plug and evaporation of the solvent gave a yellow product which was suspended in n-hexane (5 mL) and stirred for 30 minutes. The yellow solid product was collected by filtration and washed by n-hexane. Drying in vacuo afforded 215 mg of the product. Yield: 46%. ¹H NMR (400 MHz, CDCl₃): δ 7.41 (s, 1H), 7.28 (s, 1H), 7.04 (s, 2H), 6.89 (s, 1H), 2.92 (m, 2H), 2.67–2.50 (m, 1H), 2.47-2.40 (m, 1H), 2.35 (s, 3H), 2.11 (s, 3H), 2.04 (s, 3H), 2.01 (s, 3H), 1.98 (s, 3H), 1.93–1.65 (m, 4H), 1.38 (s, 18H), 1.14 (s, 3H), 1.12 (s, 3H).¹³C NMR (101 MHz, CDCl₃): δ 150.13, 142.14, 141.23, 137.43, 134.52, 134.19, 134.10, 134.01, 132.81, 127.51, 126.86, 123.89, 123.33, 122.50, 120.47, 117.94, 93.91, 83.21, 34.88, 31.55, 28.82, 27.41, 23.44, 22.34, 18.28, 15.98, 15.56, 12.49, 12.16, 3.15, 3.14. Synthesis of Catalyst I6. [0182] nBuLi (0.93 mL, 1.6 M in hexane, 1.49 mmol) was added dropwise to a precooled solution (-30°C) of [5-(3,5-ditert-butyl-phenyl)-2-methyl-6,7,8,9-tetrahydro-3H- cyclopenta[a]naphthalen-3-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (400 mg, 0.726 mmol) in Et₂O (15 mL). The mixture was allowed to warm up to the ambient temperature under stirring over 1 hour. Then, the volatiles were evaporated, and the obtained residue was suspended in n-pentane (5 mL), collected by filtration and washed with additional portion of n-pentane to afford a beige solid. This intermediate solid product was dissolved in Et₂O (9 mL) and THF (1 mL) and cooled to -30°. Solid HfCl₄ (235 mg, 0.73 mmol) was added to the resulting solution in small portions over 10 minutes. The mixture was allowed to warm up to the ambient temperature under stirring over 1 hour. Additional stirring for 12 hours 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 a yellow product which was suspended in n-hexane (5 mL) and stirred for 30 minutes. The yellow solid product was collected by filtration and washed by n-hexane. Drying in vacuo afforded 120 mg of the product. Yield: 21%. ¹H NMR (400 MHz, CDCl₃): δ 7.40 (t, J = 1.9 Hz, 1H), 7.29 (s, 1H), 7.04 (d, J = 1.8 Hz, 2H), 6.78 (s, 1H), 2.88 (m, 2H), 2.59 (m, 1H), 2.46 (m, 1H), 2.44 (s, 3H), 2.21 (s, 3H), 2.09 (s, 3H), 2.06 (s, 3H), 1.99 (s, 3H), 1.88-1.72 (m, 4H), 1.37 (s, 18H), 1.12 (s, 3H), 1.10 (s, 3H). ¹³C NMR (101 MHz, CDCl₃): δ 150.11, 141.74, 141.25, 136.11, 133.89, 133.54, 132.86, 132.45, 132.07, 124.56, 123.36, 123.31, 122.50, 122.20, 120.42, 116.01, 95.98, 84.17, 34.87, 31.55, 28.76, 27.43, 23.48, 22.33, 18.17, 15.69, 15.30, 12.32, 11.98, 3.13, 3.09. Synthesis of Catalyst I7. [0183] nBuLi (1.45 mL, 1.6 M in hexane, 2.33 mmol) was added dropwise to a precooled solution (-30°C) of (5-(anthracen-9-yl)-2-methyl-6,7,8,9-tetrahydro-3H- cyclopenta[a]naphthalen-3-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (597 mg, 1.11 mmol) in Et₂O (15 mL). The mixture was allowed to warm up to the ambient temperature under stirring over 1 hour. Then, the volatiles were evaporated, and the obtained residue was suspended in n-pentane (5 mL), collected by filtration and washed with additional portion of n-pentane to afford a beige solid. This intermediate solid product was dissolved in Et₂O (10 mL) and cooled to -30°C. Solid ZrCl₄ (261 mg, 1.12 mmol) was added to the resulting solution 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. After additional stirring for 1 hour, volatiles were evaporated, and the product was extracted into CH₂Cl₂ (15 mL). Filtration through a celite plug and evaporation of the solvent gave a crude product which was suspended in n-hexane (5 mL), filtered, washed with n-hexane (5 mL) and dried in vacuo to afford a bright yellow product. Yield: 409 mg, 53%. ¹H NMR (400 MHz, CDCl₃): δ 8.50 (s, 1H), 8.05 (dd, J = 11.7, 8.5 Hz, 2H), 7.66 (d, J = 8.7 Hz, 1H), 7.53 (d, J = 8.8 Hz, 1H), 7.51 – 7.42 (m, 2H), 7.40 – 7.19 (m, 3H), 7.02 (s, 1H), 2.99 (qt, J = 25.4, 7.1 Hz, 2H), 2.40 (s, 3H), 2.12 (s, 3H), 2.07 (s, 3H), 2.05 (s, 3H), 2.02 – 1.76 (m, 4H), 1.73 (s, 3H), 1.69 – 1.46 (m, 2H), 1.08 (s, 3H), 0.92 (s, 3H).¹³C NMR (101 MHz, CDCl₃): δ 137.55, 137.39, 136.26, 135.21, 135.19, 134.58, 134.34, 133.14, 131.39, 131.33, 130.53, 130.29, 128.39, 128.22, 128.12, 127.85, 127.74, 126.41, 126.34, 125.38, 125.36, 125.06, 123.89, 123.81, 117.91, 94.27, 84.03, 27.45, 26.98, 23.00, 22.11, 18.47, 15.89, 15.70, 12.56, 12.18, 3.02, 2.92. Synthesis of Catalyst C1. [0184] nBuLi (1.70 mL, 1.6 M in hexane, 2.72 mmol) was added to a precooled solution (-35°C) of dimethyl(2-methyl-6,7,8,9-tetrahydro-3H-cyclopenta[a]naphthalen-3-yl)(2,3,4,5- tetramethylcyclopenta-2,4-dien-1-yl)silane (510 mg, 1.29 mmol, prepared according to US 2022-0185916 Al) in Et₂O (15 mL). The mixture was allowed to warm up to the ambient temperature and stirred for additional 2 hours. Evaporation of Et₂O and washing the resulting solid product with n-pentane gave 467 mg of a light pink solid. This intermediate product was dissolved in Et₂O (10 mL) and cooled to -35°C. Solid ZrCl₄ (249 mg, 1.08 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 agitated for 1 hour 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 dispersed in n-hexane, stirred for 30 minutes and then filtered. The filtrate cake was washed with n-hexane and dried in vacuo to afford 270 mg of a yellow solid. Yield: 73%. ¹H NMR (500 MHz, CDCl₃) δ 7.33 (d, J_HH = 8.61 Hz, 1H), 6.82 (s, 1H), 6.74 (d, JHH = 8.61 Hz, 1H), 2.85-2.74 (m, 4H), 2.31 (s, 3H), 2.08 (s, 3H), 1.99 (s, 3H), 1.95-1.83 (m, 4H), 1.89 (s, 6H), 1.19 (s, 3H), 1.10 (s, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 137.55, 135.39, 134.71, 134.38, 134.33, 132.36, 127.87, 127.66, 126.95, 124.02, 121.98, 117.51, 94.00, 83.76, 29.43, 26.67, 23.08, 22.48, 18.30, 15.88, 15.59, 12.40, 12.09, 3.08, 2.98. Preparation of support material (SMAO) [0185] 12.8 g of PD17062 silica (600 deg 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. [0186] 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. [0187] 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 [0188] 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. 6,175,409; 6,260,407; 6,294,388; 6,406,632; 6,436,292; 6,454,947; 6,461,515; 6,475,391; 6,491,816; and 6,491,823; 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 [0189] Unless otherwise indicated the reactor samples were analyzed according to the GPC-4D method described above. Differential Scanning Calorimetry (DSC) [0190] Peak melting point, T_m, 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. [0191] Overall, catalyst compounds of the present disclosure can have 2-substituted 6,7,8,9- tetrahydro-cyclopenta[a]naphthalenyl moieties. Catalyst compounds of the present disclosure can have a substituted aryl moiety at the 5-position of the 6,7,8,9-tetrahydro- cyclopenta[a]naphthalenyl ring. Catalysts of the present disclosure can exhibit excellent activities, particularly for supported metallocene catalysts and particularly for forming linear low-density polyethylene (LLDPE). In addition, in the case of propylene-ethylene copolymers, metallocene catalysts having high activity of the present disclosure can provide propylene- ethylene copolymers having high molecular weight and broad polydispersity indices. Metallocene catalysts of the present disclosure can provide copolymer components with high molecular weight, broader molecular weight distribution, and increased ethylene content (as compared to conventional PE copolymers) under commercially relevant process conditions where the metallocene catalyst has high activity. Broader molecular weight distribution and increased ethylene content provides controllable impact resistance to broaden the possible uses of impact copolymers.

[0192] 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. [0193] 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.

[0194] 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.

[0195] 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 catalyst compound represented by Formula (I): wherein: M is a group 3 metal, a group 4 metal, or a 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; each of R¹, R², R³, and R⁴ is 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; each of R⁶ and R⁸ is independently hydrogen or a substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group; R⁷ is a substituted aryl group or 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 hydrocarbyl group.

2. The catalyst compound of claim 1, wherein R⁷ is a substituted aryl group represented by the formula: , wherein each of R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is independently hydrogen, a hydrocarbyl group, 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.

3. The catalyst compound of claim 1, wherein R⁷ is selected from: .

4. The catalyst compound of claim 1, wherein R⁷ is an unsubstituted naphthyl group or an unsubstituted anthracenyl group.

5. The catalyst compound of any of claim 1-4, wherein each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ is hydrogen.

6. The catalyst compound of any of claim 1-4, wherein each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.

7. The catalyst compound of any of claims 1 to 4, wherein each of R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ is independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, n-pentyl, isopentyl, and neopentyl.

8. The catalyst compound of any of claims 1 to 7, wherein T is selected from the group consisting of Si(CH₃)₂, Si(CH₂CH₃)₂, and Si(CH₂CH₂CH₃)₂.

9. The catalyst compound of any of claims 1 to 8, wherein M is zirconium or hafnium.

10. The catalyst compound of any of claims 1 to 9, wherein each of X¹ and X² is chloro or methyl.

11. The catalyst compound of any of claims 1 to 10, wherein each of R¹, R², R³, and R⁴ is methyl.

12. The catalyst compound of any of claims 1 to 11, wherein R⁵ is C₁-C₃ alkyl.

13. The catalyst compound of any of claims 1 to 12, wherein each of R⁶ and R⁸ is hydrogen.

14. The catalyst compound of claim 1, wherein: (1) M is Zr or Hf, (2) T is Si(CH₃)₂, 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 C₁-C₃ alkyl, (7) R⁷ is substituted aryl, and (8) each of X¹ and X² is chloro.

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

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

17. A catalyst compound represented by Formula (II): 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, 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 hydrocarbyl group; n is an integer of 1, 2 or 3.

18. A catalyst system comprising an activator, the catalyst compound of any of claims 1 to 17, and an optional support material.

19. 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 18, 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.

20. The process of claim 19, wherein the one or more C₂-C₂₀ alpha-olefins consists of ethylene and octene to form the alpha olefin copolymer.

21. The process of claim 20, wherein the catalyst compound has a catalyst activity of about 750 kg/mmolcat^-1hr^-1 to about 900 kg/mmolcat^-1hr^-1.

22. The process of claim 19, wherein the one or more C₂-C₂₀ alpha-olefins consists of propylene and ethylene to form the alpha olefin copolymer.

23. The process of claim 22, wherein the alpha olefin copolymer has an ethylene content of about 40 wt% to about 50 wt%.

24. The process of claim 23, wherein the alpha olefin copolymer has a weight average molecular weight (Mw) of about 140,000 g/mol to about 150,000 g/mol.

25. The process of any of claims 22 to 24, wherein the alpha olefin copolymer has an Mw/Mn (PDI) value of about 8 to about 10.