Binuclear indacene catalysts for olefin polymerization

Abstract

Disclosed herein are catalyst compounds and catalyst systems comprising organometallic metallocene catalysts having at least one binuclear indacene group. Further disclosed herein are methods of using the organometallic metallocene catalysts having at least one binuclear indacene group in polymerization such as gas-phase polymerization and slurry polymerization.

Description

BINUCLEAR INDACENE CATALYSTS FOR OLEFIN POLYMERIZATIONFIELD

[0001] The subject matter disclosed herein relates to organometallic metallocene catalysts having at least one binuclear indacene group and catalyst systems comprising an organometallic metallocene catalyst having at least one binuclear indacene group, as well as uses thereof in olefin polymerization applications.BACKGROUND

[0002] Metallocene catalysts are ubiquitous in the polyolefin industry and often feature complicated ligand scaffolds that are prepared via tedious multi-step syntheses. For these metallocene catalysts, significant diversification comes at a substantial cost penalty, which often limits the practical usage of highly complex catalysts. Additionally, while there is interest in finding new metallocene catalyst systems that enable the production of olefin polymers having specific properties, such as high melting point and high molecular weight, it is also presently recognized that certain materials used in the syntheses of metallocene catalysts may not be widely produced at scale or easily obtainable at low cost. This undesirably increases the difficulty and cost of synthesizing the metallocene catalysts, which also undesirably increases the overall cost of production of olefin polymers. Additionally, metallocene catalysts exhibit significant disadvantage in alpha olefin polymerization activities relative to conventional Ziegler-Natta systems. This is particularly relevant in propylene polymerization, where metallocene catalysts are often process incompatible due to reduced catalyst activities.SUMMARY

[0003] Disclosed herein is an example catalyst compound represented by the formula:wherein: M is a transition metal atom selected from group 3, 4, or 5 of the Periodic Table of Elements, L is a linking group selected from the group consisting of single covalent bond, C1-C20 hydrocarbylene group, and divalent ferrocene, each X is a univalent anionic ligand, or two adjacent X's comprise a C2-C20 hydrocarbylene group bound to transition metal atom M to form a metallocycle ring, or two adjacent X’s form a chelating ligand, or two adjacent X’s form a C2-C20 diene ligand; R1, R2, and R3are each independently selected from a hydrogen atom, an unsubstituted C1to C20hydrocarbyl group, or a substituted C1to C20hydrocarbyl group. R4, R5, R6and R7are each independently selected from a hydrogen atom, an unsubstituted C1to C20hydrocarbyl group, or a substituted or unsubstituted C1to C20hydrocarbyl group, and J1and J2are fused to form a C1-C20cyclic ring.

[0004] Further disclosed herein is an example catalyst system including an activator and a catalyst compound represented by the formula:wherein: M is a transition metal atom selected from group 3, 4, or 5 of the Periodic Table of Elements, L is a linking group selected from the group consisting of single covalent bond, C1-C20 hydrocarbylene group, and divalent ferrocene, each X is a univalent anionic ligand, or two adjacent X's comprise a C2-C20 hydrocarbylene group bound to transition metal atom M to form a metallocycle ring, or two adjacent X’s form a chelating ligand, or two adjacent X’s form a C2-C20 diene ligand; R1, R2, and R3are each independently selected from a hydrogen atom, an unsubstituted C1to C20hydrocarbyl group, or a substituted C1to C20hydrocarbyl group. R4, R5, R6and R7are each independently selected from a hydrogen atom, an unsubstituted C1to C20hydrocarbyl group, or a substituted or unsubstituted C1to C20hydrocarbyl group, and J1and J2are fused to form a C1-C20cyclic ring.

[0005] Further disclosed herein is a method comprising: introducing one or more of a C2 to C20 olefin monomer, and a catalyst system disclosed herein, and optionally hydrogen into a reactor at a reactor pressure of from 0.7 bar to 70 bar and a reactor temperature of from 20°C to 150°C; and polymerizing the C2 to C20 olefin monomer to obtain a polymer or copolymer.

[0006] These and other features and attributes of the disclosed methods and systems of the present disclosure and their advantageous applications and / or uses will be apparent from the detailed description which follows.BRIEF DESCRIPTION OF THE DRAWINGS

[0007] To assist those of ordinary' skill in the relevant art in making and using the subject matter hereof, reference is made to the appended drawings, wherein:

[0008] FIG. 1 is a set of chemical structures representing embodiments II, 12, 13, 14, 15, 16, 17, and 18 of julolidine substituted metallocene catalyst compounds, in accordance with certain embodiments of the present disclosure.

[0009] FIG. 2 is a set of chemical structures representing comparative catalysts Ci, C2, C3, C4, C5, Ce, C7, Cs, and C9, in accordance with certain embodiments of the present disclosure.

[0010] FIG. 3 is a general synthetic synthesis scheme for julolidine-based catalysts, in accordance with certain embodiments of the present disclosure.

[0011] FIG. 4 is a general synthetic synthesis scheme for julolidine-based catalysts, in accordance with certain embodiments of the present disclosure.

[0012] FIG. 5 is a bar graph comparing polypropylene activity in kg / mmol*h for julolidine substituted metallocene catalyst compounds, in accordance with certain embodiments of the present disclosure.

[0013] FIG. 6 is a bar graph comparing ethylene-polypropylene copolymer activity in kg / mmol*h for julolidine substituted metallocene catalyst compounds, in accordance with certain embodiments of the present disclosure.DETAILED DESCRIPTION

[0014] Disclosed herein are catalyst compounds and catalyst systems comprising organometallic metallocene catalysts having at least one binuclear indacene group. Further disclosed herein are methods of using the organometallic metallocene catalysts having at least one binuclear indacene group in polymerization such as gas-phase polymerization and slurry polymerization.

[0015] As used herein, the indefinite article “a’' or “an” shall mean “at least one” unless specified to the contrary or the context clearly indicates otherwise. Thus, embodiments using “an alpha-olefin” include embodiments where one, two or more alpha-olefins are used, unless specified to the contrary' or the context clearly indicates that only one alpha-olefin is used.

[0016] As used herein, “wt.%” means percentage by weight, “vol%” means percentage by volume. “mol%” means percentage by mole, “ppm” means parts per million, and “ppm wt” and “wppm” are used interchangeably and mean parts per million on a weight basis. All concentrations herein, unless otherwise stated, are expressed on the basis of the total amount of the composition in question.

[0017] An “olefin” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as including an olefin, e.g., ethylene and at least one C3to C20α-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 repeating unit / mer unit or simply unit in the copolymer is derived from ethylene in the polymerization reaction and the derived units are present at 35 wt.% to 55 wt.%. based on a weight of the copolymer. For the purposes of the present disclosure, ethylene shall be considered an a-olefin.

[0018] A “polymer” has two or more of the same or different repeating units / mer units or simply units. A “homopolymer” is a polymer having units that are the same. A “copolymer” is a polymer having two or more units that are different from each other. A “terpolymer” is a polymer having three units that are different from each other. The term “different” as used to refer to units indicates that the units differ from each other by at least one atom or are different isomerically. The definition of copolymer, as used herein, includes terpolymers and the like. Likewise, the definition of polymer, as used herein, includes homopolymers, copolymers, and the like. Furthermore, the terms “polyethylene copolymer”, “ethylene copolymer”, and “ethylene-based polymer” are used interchangeably to refer to a copolymer that includes at least 50 mol% of units derived from ethylene.

[0019] Nomenclature of elements and groups thereof used herein are pursuant to the NEW NOTATION published in HAWLEYS CONDENSED CHEMICAL DICTIONARY, Thirteenth Edition, John Wiley & Sons, Inc., (1997) (reproduced there with permission from IUPAC), unless reference is made to the Previous IUPAC form noted with Roman numerals (also appearing in the same), or unless otherwise noted.

[0020] As used herein, the term “catalyst system” refers to a combination of at least one catalyst compound, an optional activator, an optional co-activator. and an optional support material. As such, in some embodiments the catalyst system can include only a single catalyst compound when the optional activator, the optional co-activator, and the optional support material are not present. In other embodiments, the catalyst system can include only two or more catalyst compounds when the optional activator, the optional co-activator, and the optional support material are not present. For the purposes of the present disclosure, 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. Catalyst systems, catalysts, and activatorsof the present disclosure are intended to embrace ionic forms in addition to the neutral forms of the compounds / components.

[0021] A metallocene catalyst is an organometallic compound with at least one K-bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) and more frequently two %-bound cyclopentadienyl moieties or substituted cyclopentadienyl moieties bonded to a transition metal. In the description herein, the metallocene catalyst may be described as a catalyst precursor, a pre-catalyst compound, metallocene catalyst compound or a transition metal compound, and these terms are used interchangeably. An “anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion. For purposes of the present disclosure, in relation to metallocene catalyst compounds, the term “substituted” means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group. For example, methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group.Catalyst Compounds

[0022] Embodiments of the catalysts disclosed herein are organometallic metallocene catalysts comprising at least one binuclear indacene group. Relative to previously utilized indenyl based binuclear catalysts, the catalysts of the present disclosure provide greater polymerization activities and improved polypropylene melting points. Further, phenyl linked binuclear indacene embodiments also provide improvement in molecular weights of ethylenepropylene copolymers relative to both mononuclear and binuclear indenyl.

[0023] Embodiments of the organometallic metallocene catalysts comprising at least one binuclear indacene group described herein are generally represented by Structure 1.

[0024] In Structure 1, M is a transition metal atom selected from group 3, 4, or 5 of the Periodic Table of Elements. In embodiments, M is zirconium.

[0025] In Structure 1 L is a linking group selected from a single covalent bond, a C1-C20 hydrocarbylene group, or divalent ferrocene. In embodiments the linking group L, comprising the C1-C20 hydrocarbylene group, may be linear, branched, cyclic, aromatic, or include substituent moieties which include one or more of linear, branched, cyclic, and / or aromatic components. In embodiments, the C1-C20 hydrocarbylene group includes a divalent aryl group, a C1-C20 substituted divalent aryl group, a divalent fluorenyl group, a C1-C20 substituted divalent fluorenyl group, a divalent naphthalene group, a C1-C20 substituted divalent naphthalene group, a divalent bi-phenyl group, or a C1-C20 substituted divalent bi-phenyl group. In embodiments, substitutions include hydrocarbyl groups (R) such a methyl, ethyl, propyl, isopropyl, tertbutyl, isobutyl, neopentyl, hexyl, and / or -OR, -NR2, or -SR heteroatom functionalities.

[0026] In Structure 1, T is an optional bridging group wherein T is represented by the formula: (R*2G)g, where each G is C, Si, or Ge, g is 1 or 2, and each R* is, independently, hydrogen, halogen, Ci to C20 linear, branched, cyclic, or aromatic hydrocarbyl or a substituted Ci to C20 linear, branched, cyclic, or aromatic hydrocarbyl. In some embodiments, T is silylene or silylene substituted with two groups independently selected from hydrogen and Ci to C20linear, branched, cyclic, or aromatic hydrocarbyl. In some embodiments T is not present and the catalyst is unbridged. In embodiments T is represented by R'2C, R'2Si, R'2Ge, R2CCR2, 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'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'2CR2C— Se— CR'2CR’2, R'2C— Se— CR2CR2, 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', or R'2C — PR' — CR'2, where each R' is, independently, hydrogen or a Ci to C20 containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl. silylcarbyl or germylcarbyl substituent and, optionally, two or more adjacent R's may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. In some embodiments T may be selected from CH2, CH2CH2, C(CH3)2, SiMe2, SiPh2, SiMePh, silylcyclobutyl (Si(CH2)3), SiPh2, (Ph)2C, (p-(Et)3SiPh)2C, and cyclopentasilylene (Si(CH2)4).

[0027] In Structure 1, each X is a univalent anionic ligand, or two adjacent X’s comprise a C2-C20 hydrocarbylene group bound to a transition metal atom M to form a metallocycle ring, and / or adjacent X’s form a chelating ligand, and / or a C2-C20 diene ligand. In embodiments, halogens, or Ci-Ce hydrocarbyl, or a hydride ligand. In embodiments, the chelating ligand includes ethylenediamine, bipyridyl, 1,2-bis diphenylphosphino ethane, acetate, oxolate, acetylacetonate, tri azacyclononane, tris(phyrazolyl)borate, terpyridine, porphyrin, corrole, tris(2-aminoethyl)amine, 12-crown-4, 15-crown-5, 18-crown-6, [2.2.2.]ciyptand, and / or ethylenediaminetetraacetate.

[0028] In Structure 1, each of R1- R3are each independently selected from a hydrogen atom, a substituted C1to C20hydrocarbyl group, or unsubstituted C1to C20hydrocarbyl group.

[0029] In Structure 1, each of R4, R5, R6and R7are each independently selected from a hydrogen atom or a substituted or unsubstituted C1to C20hydrocarbyl group, and optionally; R4and R5are joined to form a cyclic structure.

[0030] In Structure 1, J1and J2are fused to form a C1-C20cyclic ring. In further embodiments, J1and J2are fused to form at least one of 1,5,6,7-tetrahydro-s-indacenide, 6,6-dimethyl-l,5,6,7-tetrahydro-s-indacen-l-ide, 5,5,7,7-tetramethyl-l,5,6,7-tetrahydro-s-indacen-l-ide, 5,6,7,8-tetrahydro-lH-cyclopenta[b]naphthalen-l-ide, 5,6,7,8-tetrahydro-lH-5,8-methanocyclopenta[b]naphthalen-l-ide, 5,6,7,8-tetrahydro-lH-5,8-ethanocyclopenta[b]naphthalen-l-ide, 5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-lH-cyclopenta[b]naphthalen-l -ide, or 1,5,6,7,8,9-hexahydrocyclohepta[f]inden- 1 -ide.

[0031] A non-limiting set of example organometallic metallocene catalysts comprising at least one binuclear indacene group (Catalyst I1-I7) are illustrated in FIG. 1 which were synthesized and compared against a number of comparative metallocene catalysts (C1-C9) illustrated in FIG. 2.Representative Synthesis

[0032] FIG. 3 is a general synthetic synthesis scheme for embodiments of the I1-I7 organometallic metallocene catalysts comprising at least one binuclear indacene group. In FIG. 3, the term “Ar” represents any di-boronic acid, such as diphenyl, dinaphtyl or ferrocene.Activators

[0033] The terms “cocatalyst” and “activator” are used herein interchangeably and are defined to be any compound which can activate any one of the organometallic metallocene catalysts comprising at least one binuclear indacene group described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation. Non-limiting activators, for example, include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts. For various embodiments disclosed herein, the activators typically include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, o-bound, metal ligand making the metal complex cationic and providing a charge-balancing non-coordinating or weakly coordinating anion.

[0034] In one embodiment, alumoxane activators are utilized as an activator in the catalyst composition. Alumoxanes are generally oligomeric compounds containing — Al(R') — O — sub-units, where R1is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, and isobutyl alumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide, or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. In some embodiments, it may be desirable 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 3 A).

[0035] When the activator is an alumoxane (modified or unmodified), some embodiments select the maximum amount of activator typically at up to a 5000-fold molar excess Al / M over the catalyst compound (per metal catalytic site). The minimum activator-to-catalyst-compound is a 1:1 molar ratio. In certain embodiments, the activator-to-catalyst-compound molar ratio ranges from 1:1 to 500:1, from 1:1 to 200:1, from 1:1 to 100:1, or from 1:1 to 50:1. In certain embodiments, the aluminum of the aluminoxane activator is present in molar ratios of about 1: 100 to about 1:2000 relative to the transition metal M (selected from group 3, 4, or 5 of the Periodic Table of Elements. In an alternate embodiment, little or no alumoxane is used in the polymerization processes described herein. In some embodiments, alumoxane is present at zero molar percent (e.g., 0 mol %). In other embodiments, alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal less than 500:1, less than 300:1, less than 250:1, less than 100:1. or less than 1:1.

[0036] The term ’‘non-coordinating anion” (NCA) means an anion that either does not coordinate to a cation or that is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a neutral 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 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 this 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.

[0037] For example, in certain embodiments, a NCA activator may be represented by the formula: (Z)d+(Ad-). In an embodiment of this formulation, Z is (L-H)+ or a reducible Lewis Acid; L is a Lewis base; H is hydrogen; (L-H)+ is a Bronsted acid; Ad- is a non-coordinating anion having charge d-; and d is an integer from 1 to 3. In another embodiment of this formulation, Ad- is a non-coordinating anion having charge d-; d is an integer from 1 to 3; and Z is a reducible Lewis acid represented by the formula: (Ar3C+). wherein Ar is aryl or aryl substituted with a heteroatom, a Ci to C40 hydrocarbyl, or a substituted Ci to C40 hydrocarbyl.

[0038] It is within the scope of this disclosure to use an ionizing or stoichiometric activator, neutral or ionic, such as tri (n-butyl) ammonium tetrakis(pentafluorophenyl)borate, a tris perfluorophenyl boron metalloid precursor or a tris perfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anions, boric acid, or combination thereof. It is also within the scope of this disclosure to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.

[0039] Examples of neutral stoichiometric activators include tri-substituted boron, tellurium, aluminum, gallium, and indium, or mixtures thereof. The three substituent groups are each independently selected from alkyls, alkenyls, halogens, substituted alkyls, aryls, arylhalides, alkoxy, and halides. In some embodiments, the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds, and mixtures thereof. This can include alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and aryl groups having 3 to 20 carbon atoms (including substituted aryls). In certain embodiments, the three groups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl, or mixtures thereof. In other embodiments, the three groups include halogenated (e g., fluorinated) groups and aryl groups. For some embodiments, a neutral stoichiometric activator, such as tris perfluorophenyl boron or tris perfluoronaphthyl boron, may be used.Support Materials

[0040] In embodiments herein, the organometallic metallocene catalysts comprising at least one binuclear indacene group may be disposed on an inert support material to form a catalyst system. The support material is a porous support material, for example, talc or inorganic oxides. Other support materials include zeolites, clays (e.g., silica clays, silicon oxide clay mixtures), organoclays, or any other organic or inorganic support material and the like, or mixtures thereof.

[0041] In general, the support material is an inorganic oxide in a finely divided form. Suitable inorganic oxide materials for use in metallocene catalyst systems herein include Groups 2, 4, 13, and 14 metal oxides, such as silica (SiO₂), alumina (Al₂O₃), and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with silica or alumina include magnesia, titania (TiO₂), zirconia (ZrO₂), and the like. Other suitable support materials, however, can be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene. Examples of useful supports include, but are not limited to, magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Also, combinations of these support materials may be used, for example, silicachromium, silica-alumina, silica-titania, and the like. In some embodiments, support materials include Al₂O₃, ZrO₂, SiO₂, and combinations thereof, while in other embodiments, the support material includes SiO₂, Al₂O₃, or SiO₂ / Al₂O₃.

[0042] It is generally desirable for the support material (e.g., an inorganic oxide) to have a surface area that ranges from 10 to 700 square meters per gram (m2 / g), a pore volume that ranges from 0.1 to 4.0 cubic centimeters per gram (cc / g), and an average particle size thatranges from 5 to 500 micrometers (μm). In some embodiments, the surface area of the support material ranges from 50 to 500 m2 / g, the pore volume ranges from 0.5 to 3.5 cc / g, and the average particle size ranges from 10 to 200 μm. In other embodiments, the surface area of the support material ranges from 100 to 400 m2 / g, the pore volume ranges from 0.8 to 3.0 cc / g, and the average particle size ranges from 5 to 100 μm. In general, the average pore size of the support material ranges from 10 to 1000 Angstroms (A), such as between 50 and 500 A, or between 75 and 350 A. In some embodiments, the support material is a high surface area, amorphous silica having a surface area of 300 m2 / g and a pore volume of 1.65 cc / g.

[0043] The support material should be dry, that is, substantially or entirely free of absorbed water. Drying of the support material can be achieved by heating or calcining in a temperature range of 150°C to 1000°C (e.g., a temperature greater than 200°C). For example, when the support material is silica, it is heated to at least 200°C (e.g.. between 200°C and 850°C, or at 600°C) for a period of time ranging from 1 minute to 100 hours (e.g., from 12 hours to 72 hours, or from 24 hours to 60 hours). In certain embodiments, the calcined support material includes reactive surface groups (e.g., at least some reactive hydroxyl (OH) groups) to produce supported catalyst systems.

[0044] The calcined support material is subsequently contacted with at least one polymerization catalyst comprising at least one organometallic metallocene catalysts comprising at least one binuclear indacene group and an activator. Optionally a promoter such as other trialkylaluminum compound may be added to any of the steps. For example, in certain embodiments, the support material is slurried in a non-polar solvent, and the resulting slurry is subsequently contacted with a solution of organometallic metallocene catalysts comprising at least one binuclear indacene group and an activator. In some embodiments, the slurry of the support material is first contacted with the activator and a tri alkyl aluminum promoter for a period of time ranging from 0.1 hours to 24 hours (e.g., from 2 hours to 16 hours, or from 4 hours to 8 hours). For such embodiments, the solution of the organometallic metallocene catalysts comprising at least one binuclear indacene group is then contacted with the isolated support / activator. In certain embodiments, the supported catalyst system is generated in situ. In an alternate embodiment, the slurry of the support material is first contacted with the catalyst compound for a period of time ranging from 0.1 hours to 24 hours (e.g., from 2 hours to 16 hours, or from 4 hours to 8 hours) before the slurry of the supported metallocene compound is contacted with the activator solution.

[0045] In certain embodiments, the mixture of the organometallic metallocene catalysts comprising at least one binuclear indacene group, activator, and support is heated in thetemperature range of 0°C to 70°C (e.g., between 23°C and 60°C, at room temperature) for a contact time period. In general, the contact time period ranges from 0.1 hours to 24 hours (e.g., between 2 and 16 hours, or between 4 and 8 hours).

[0046] Suitable non-polar solvents are materials in which all of the reactants used herein (e.g., the activator and the metallocene compound) are at least partially soluble and are liquid at reaction temperatures. A non-limiting list of example non-polar solvents includes: alkanes (e.g., isopentane, hexane, n-heptane. octane, nonane, and decane), cycloalkanes (e.g., cyclohexane), aromatics (e.g., benzene, toluene, and ethylbenzene).Polymerization Process

[0047] The present disclosure relates to embodiments of polymerization processes in which a monomer (such as propylene), and, optionally, a comonomer, are contacted with a catalyst system that includes at least an activator and at least one organometallic metallocene catalyst comprising at least one binuclear indacene group, as described above. The catalyst compound and activator may be combined in any order, and are typically combined prior to contacting the monomer.

[0048] Monomers useful herein include substituted or unsubstituted C2 to C40 alpha olefins, such as C2 to C20 alpha olefins or C2 to C12 alpha olefins or dienes (e.g., ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof). In certain embodiments, the monomer includes propylene and optional comonomers, including one or more ethylene or C4 to C40 olefins (e.g., C4 to C20 olefins, or O, 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. In another embodiment, the monomer includes ethylene and optional comonomers, including one or more C3 to C40 olefins, C4 to C20 olefins, or Ce 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.

[0049] A non-limiting list of example C2 to C40 olefin monomers and optional comonomers includes: ethylene, propylene, 1 -butene, 1 -pentene, 1 -hexene, 1 -heptene, 1 -octene, nonene, 1 -decene, undecene, dodecene. norbomene, norbomadiene, di cyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, 2-methyl-l -pentene, vinylcyclobutane, 1, -hexadiene, 1,7-octadiene, 1,9-decadiene, substituted derivatives thereof, and isomers thereof. In certain embodiments, a non-limiting list of example C2 to C40 olefin monomers and optional comonomers includes:hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, l-hydroxy-4-cyclooctene, 1 -acetoxy -4-cyclooctene, 5 -methylcyclopentene, cyclopentene, dicyclopentadiene, norbomene, norbomadiene, and their respective homologs and derivatives. In certain embodiments, anon-limiting list of example C2 to C40 olefin monomers and optional comonomers includes norbomene, norbomadiene, and dicyclopentadiene.

[0050] Polymerization processes disclosed herein can be carried out in any manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process known in the art can be used. Such processes can be run in a batch, semi-batch, or continuous mode. For some embodiments, homogeneous polymerization processes and slurry processes are used, wherein a homogeneous polymerization process is defined to be a process where at least 90 wt.% of the product is soluble in the reaction media. In other embodiments, a bulk homogeneous polymerization process is used, wherein a bulk process is defined to be a process where monomer concentration in all feeds to the reactor is 70% or more by volume. In alternative embodiments, no substantial 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 typically found with the monomer (e.g., propane in propylene). In another embodiment, the process is a slurry polymerization process, wherein a supported catalyst is employed, and monomers are polymerized on the supported catalyst particles. For some embodiments, at least 95 wt.% of polymer products derived from the supported catalyst are in granular form as solid particles (e.g., not dissolved in the diluent or solvent).

[0051] Suitable diluents / solvents for polymerization include non-coordinating, inert liquids. Examples include straight and branched-chain hydrocarbons (e.g., isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof); cyclic and alicyclic hydrocarbons (e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as Isopar™; perhalogenated hydrocarbons (e.g., perfluorinated C4 to C10 alkanes, and chlorobenzene), and aromatic and alkylsubstituted aromatic compounds (e.g, benzene, toluene, mesitylene, and xylene). Suitable solvents also include liquid olefins that may act as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-l-pentene, 4-methyl-l -pentene, 1-octene, 1-decene, and mixtures thereof. In certain embodiments, aliphatic hydrocarbon solvents (e.g., isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof) and / or cyclic and alicyclic hydrocarbons (e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof) are used. In other embodiments, the solvent is not aromatic or includes less than 1 wt.% aromatic solvents, lessthan 0.5 wt.% aromatic solvents, or 0 wt.% aromatic solvents. In an example embodiment, the feed concentration of the monomers and comonomers for the polymerization is 60 vol% solvent or less (e.g.. 40 vol% or less, or 20 vol% or less), based on the total volume of the feedstream (e.g., as part of a bulk homogeneous polymerization process).

[0052] The polymerization can be run at any suitable temperature and / or pressure to obtain the desired ethylene polymers. For example, in certain embodiments, the polymerization may be performed in the temperature range from 0°C to 300°C (e.g., from 10°C to 200°C, from 20°C to 150°C, from 40°C to 120°C, from 45°C to 80°C). Additionally, in certain embodiments, the polymerization is performed in the pressure range from 0.05 megapascal (MPa) to 10 MPa (e.g., from 0.07 MPa to 7 MPa, from 0.45 MPa to 6 MPa, or from 0.5 MPa to 4 MPa). In certain embodiments, the run time of the polymerization reaction is up to 300 minutes (e.g., from 5 minutes to 250 minutes, or from 10 minutes to 120 minutes).Polyolefin Products

[0053] This disclosure also relates to compositions of matter produced by the methods described herein.

[0054] The disclosed polymerization process produces olefin polymers, such as polyethylene, polypropylene homopolymers, and polypropylene copolymers. In a one embodiment, the polymers produced herein are copolymers of ethylene having from 0 mol% to 50 mol% (e.g., from 0.5 mol% to 50 mol%, from 1 mol% to 30 mol%, from 5 mol% to 10 mol%) of one or more C3 to C20 olefin comonomers (e.g., a C3 to C12 alpha-olefin, such as propylene, butene, hexene, octene, decene. or dodecene). For some embodiments, the one or more C3 to C20 olefin comonomers may be propylene, butene, hexene, or octene. In another embodiment, the polymers produced herein are copolymers of propylene having from 0 mol% to 50 mol% (e.g., from 0.5 mol% to 50 mol%, from 1 mol% to 30 mol%, from 5 mol% to 10 mol%) of one or more of C2 or C4 to C20 olefin comonomer (e.g., a C4 to C12 alpha-olefin, such as ethylene, butene, hexene, octene, decene, or dodecene). For some embodiments, the one or more C2 or C4 to C20 olefin comonomer may be ethylene, butene, hexene, or octene. For certain embodiments, the propylene polymers produced may be isotactic polypropylene, atactic polypropylene having random, block, or impact copolymers.

[0055] In some embodiments, the olefin polymer products are homopolymers or copolymers having a mean molecular weight (Mw) from 1,000 grams per mole (g / mol) to 1,000,000 g / mol, from 5,000 g / mol to 500,000 g / mol, or from 10,000 g / mol to 250,000 g / mol, as measured by gel permeation chromatography. In some embodiments, these homopolymers or copolymers have a Mw distribution with poly dispersity index less than 10, less than 6, orless than 3. In some embodiments, these homopolymers or copolymers have a melting point (Tm) at a point in a range of 120°C to 200°C. In some embodiments, a copolymer product has a comonomer content of 0.01 wt.% - 99.99 wt.%. Alternatively, from 0.1 wt.% to 50 wt.% (e.g., from 1 wt.% to 35 wt.%, from 2 to 20 wt.%, or from 3 wt.% to 10 wt.%).End Uses

[0056] The polymers produced by the processes disclosed herein and blends thereof can be useful in forming operations such as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding, and rotary molding. Films include blown or cast films formed by co-extrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc., in food-contact and non-food contact applications. Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc. Extruded articles include medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.

[0057] Specifically, any of the foregoing polymers, such as ethylene copolymers or blends thereof, can be used in 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.

[0058] The polymers produced herein may be further blended with one or more second polymers and used in film, molded part and other ty pical applications. In one embodiment, the second polymer can be selected from ethylene homopolymer, ethylene copolymers, and blends thereof. Useful second ethylene copolymers can include one or more comonomers in addition to ethylene and can be a random copolymer, a statistical copolymer, a block copolymer, and / or blends thereof. The process of making the second ethylene polymer is not critical, as it can be made by slurry, solution, gas phase, high pressure or other suitable processes, and by using catalyst systems appropriate for the polymerization of polyethylene, such as Ziegler-Natta-typecatalysts, chromium catalysts, metallocene-type catalysts, other appropriate catalyst systems or combinations thereof, or by free-radical polymerization.Additional Embodiments

[0059] Accordingly, the present disclosure may provide methods of preparing metallocene catalyst compounds and catalyst systems comprising at least one julolidine substitution. The methods and systems may include any of the various features disclosed herein, including one or more of the following embodiments.

[0060] Embodiment 1. A catalyst compound represented by the formula:wherein: M is a transition metal atom selected from group 3, 4, or 5 of the Periodic Table of Elements, L is a linking group selected from the group consisting of single covalent bond, C1-C20 hydrocarbylene group, and divalent ferrocene, each X is a univalent anionic ligand, or two adjacent X's comprise a C2-C20 hydrocarbylene group bound to transition metal atom M to form a metallocycle ring, or two adjacent X’s form a chelating ligand, or two adjacent X’s form a C2-C20 diene ligand; R1, R2, and R3are each independently selected from a hydrogen atom, an unsubstituted Ci to C20 hydrocarbyl group, or a substituted Ci to C20 hydrocarbyl group. R4, R5, R6and R7are each independently selected from a hydrogen atom, an unsubstituted Ci to C20 hydrocarbyl group, or a substituted or unsubstituted Ci to C20 hydrocarbyl group, and Ji and J2 are fused to form a C1-C20 cyclic ring.

[0061] Embodiment 2. The catalyst compound of Embodiment 1, wherein M is zirconium.

[0062] Embodiment 3. The catalyst compound of any of Embodiments 1-2, wherein each X is chloride.

[0063] Embodiment 4. The catalyst compound of any of Embodiments 1-3, wherein L is the C1-C20 hydrocarbylene group and wherein L further comprises a linker group selected from the group consisting of divalent aryl group, C1-C20 substituted divalent aryl group, divalent fluorenyl group, C1-C20 substituted divalent fluorenyl group, divalent naphthalene group, and C1-C20 substituted divalent naphthalene group.

[0064] Embodiment 5. The catalyst compound of any of Embodiments 1-3, wherein L is the C1-C20 hydrocarbylene group and wherein L further comprises a linker group selected from the group consisting of divalent bi-phenyl group and C1-C20 substituted divalent bi-phenyl group.

[0065] Embodiment 6. The catalyst compound of any of Embodiments 1-5, wherein the catalyst compound is unbridged and T is not present.

[0066] Embodiment 7. The catalyst compound of any of Embodiments 1-5 wherein: T is represented by the formula (R*2G)g, each G is C, Si, or Ge, g is 1 or 2, and each R* is, independently selected from hydrogen, halogen, Ci to C20 hydrocarbyl, or Ci to C20 substituted hydrocarbyl.

[0067] Embodiment 8. The catalyst compound of Embodiment 7, wherein two or more R* form an aromatic or a partially saturated or saturated cyclic or fused ring system.

[0068] Embodiment 9. The catalyst compound of any of Embodiments 1-8. wherein R4and R5are joined to form a cyclic structure.

[0069] Embodiment 10. The catalyst compound of any of Embodiments 1-9 wherein Ji and J2 are fused to form a compound selected from the group consisting of 1,5,6, 7-tetrahydro-s-indacenide, 6,6-dimethyl-l,5,6,7-tetrahydro-s-indacen-l-ide, 5.5,7,7-tetramethyl-l,5,6,7-tetrahydro-s-mdacen-l-ide, 5.6,7,8-tetrahydro-lH-cyclopenta[b]naphthalen-l-ide, 5, 6, 7, 8-tetrahydro-lH-5,8-methanocyclopenta[b]naphthalen-l-ide, 5,6,7,8-tetrahydro-lH-5,8-ethanocyclopenta[b]naphthalen-l-ide, 5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-lH-cyclopenta[b]naphthalen-l-ide, l,5,6,7,8,9-hexahydrocyclohepta[f|inden-l-ide, and combinations thereof.

[0070] Embodiment 11. The catalyst compound of Embodiment 1 wherein the catalyst compound is represented by any one of the following structures:

[0071] Embodiment 12. A catalyst system comprising an activator and a catalyst compound represented by the formula:wherein: M is a transition metal atom selected from group 3, 4, or 5 of the Periodic Table of Elements, L is a linking group selected from the group consisting of single covalent bond, C1-C20 hydrocarbylene group, and divalent ferrocene, each X is a univalent anionic ligand, or two adjacent X's comprise a C2-C20 hydrocarbylene group bound to transition metal atom M to form a metallocycle ring, or two adjacent X’s form a chelating ligand, or two adjacent X’s form a C2-C20 diene ligand; R1, R2, and R3are each independently selected from a hydrogen atom, an unsubstituted C1to C20hydrocarbyl group, or a substituted C1to C20hydrocarbyl group. R4, R5, R6and R7are each independently selected from a hydrogen atom, an unsubstituted C1to C20hydrocarbyl group, or a substituted or unsubstituted C1to C20hydrocarbyl group, and J1and J2are fused to form a C1-C20cyclic ring.

[0072] Embodiment 13. The catalyst system of Embodiment 12, wherein the catalyst compound is unbridged and T is not present or wherein: T is represented by the formula (R*2G)g, each G is C, Si, or Ge, g is 1 or 2. and each R* is, independently selected from hydrogen, halogen, Ci to C20 hydrocarbyl, or Ci to C20 substituted hydrocarbyl, and optionally, wherein two or more R* form an aromatic or a partially saturated or saturated cyclic or fused ring system.

[0073] Embodiment 14. The catalyst system of any of Embodiments 12-13, wherein R4and R5are joined to form a cyclic structure.

[0074] Embodiment 15. The catalyst system of any of Embodiments 12-14, wherein the activator comprises at least one of aluminoxane or salts of non-coordinating anions.

[0075] Embodiment 16. The catalyst system of Embodiment 15, wherein the salts of noncoordinating anions is represented by the formula: (Z)d+ (Ad-) wherein Z is (L-H) or a reducible Lewis Acid, L is a Lewis base; H is hydrogen; (L-H)+ is a Bronsted acid; Ad- is a non-coordinating anion having charge d-; and d is an integer from 1 to 3.

[0076] Embodiment 17. The catalyst system of Embodiment 15, wherein salts of noncoordinating anions is represented by the formula: (Z)d+ (Ad-) wherein Ad- is a noncoordinating anion having a charge d-; d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the formula: (Ar3C+), and wherein Ar is aryl or ary l substituted with a heteroatom, a Ci to C40 hydrocarbyl, or a substituted Ci to C40 hydrocarbyl.

[0077] Embodiment 18. The catalyst system of Embodiment 13, wherein the activator comprises aluminoxane and the aluminoxane is present in a ratio of about 1: 100 to about 1:2000 relative to M.

[0078] Embodiment 19. The catalyst system of any of Embodiments 12-18, further comprising a support material selected from the group consisting of Al₂O₃, ZrO₂, SiO₂, SiO₂ / Al₂O₃, SiO₂ / TiO₂, silica clay, silicon oxide / clay, and combinations thereof.

[0079] Embodiment 20. The catalyst system of Embodiment 12 wherein the catalyst compound is represented by any one of the following structures:

[0080] Embodiment 21. A method comprising: introducing one or more of a C2 to C20 olefin monomer, and a catalyst system of any one of Embodiments 12-20, and optionally hydrogen into a reactor at a reactor pressure of from 0.7 bar to 70 bar and a reactor temperature of from 20°C to 150°C; and polymerizing the C2 to C20 olefin monomer to obtain a polymer or copolymer.

[0081] Embodiment 22. The method of Embodiment 21 wherein the C2to C20olefin monomer comprises at least one monomer selected from the group consisting of ethylene, propylene 1 -butene, 1 -pentene, 1 -hexene, 2-methyl-l -pentene, vinylcyclobutane, 1 -heptene, 1 -octene, 1 -decene, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene, norbomene, vinylnorbomene, ethylidine norbomene, and combinations thereof.

[0082] Embodiment 23. The method of any of Embodiments 20-21, wherein the polymer or copolymer has a Mw value of 1,000 to 1,000,000 g / mol as measured by gel permeation chromatography.

[0083] Embodiment 24. The method of any of Embodiments 20-22, wherein the polymer or copolymer has a Mw distribution with poly dispersity index less than 10.

[0084] Embodiment 25. The method of any of Embodiments 20 to 24, wherein the polymer or copolymer has a melting point at a point in a range of about 120°C to about 200°C.Example 1

[0085] In this example, synthetic procedures that were used to prepare embodiments of the organometallic metallocene catalysts comprising at least one binuclear indacene group ( / .e., 11-15 and 17) discussed above. Each of these synthetic procedures include at least proton Nuclear Magnetic Resonance f1H NMR) spectrum characterization data collected using a 400-megahertz (MHz) spectrometer in the indicated deuterated solvent.Synthesis of Catalyst IX

[0086] To begin synthesis of II, a precursor chemical 6-methyl-8-[4-(6-c-l, 2,3,7-tetrahydro-s-indacen-4-yl)phenyl]-l,2,3,5-tetrahydro-s-indacene as in Structure 2 was prepared.

[0087] 0.275 g zirconium tetrachloride (1.18 mmol, 2 eq) was slurried into lOmL Et20.0.500 g [4-[3-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]phenyl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane tetralithiate (0.589 mmol, leq) was also slurried in a separate lOmL Et^20. The lithium salt was then added slowly into the ZrC14 slurry7. The reaction was then stirred overnight. In the morning, the solvent was removed. The residual solid was stirred in 20 mL pentane for 1 hour, filtered, and dried. The collected solid was then stirred in 20 mL dichloromethane for 1 hour and filtered to remove LiCl. The dichloromethane was then removed to give pure product. Yield was calculated as 0.460 g (72%).

[0088] The 1H NMR of Structure 2 was determined to be (400 MHz, Methylene Chloride- d2) 58.03 - 7.26 (m, 6H), 6.94 - 6.59 (m, 2H), 3.88 - 2.60 (m, 12H), 2.28 - 2.23 (m, 6H), 2.07 (m, 6H), 1.99 - 1.95 (m, 12H), 1.91 (m, 6H). 1.24 (s, 6H), 1.12 (s, 6H).

[0089] Next, 6-methyl-8-[4-(6-c-l, 2,3, 7-tetrahydro-s-indacen-4-yl)phenyl]-l, 2,3,5- tetrahydro-s-indacene dilithiate as in Structure 3 was prepared.Structure 3

[0090] In a 50 mL bomb flask, 1.65 g 8-bromo-6-methyl-l,2,3,5-tetrahydro-s-indacene (6.65 mmol, 2.2 eq), 0.5 g benzene-l,4-diboronic acid (3.02 mmol, 1 eq), 0.043 g Pd(dba)2(0.075 mmol, 0.025 eq). 0.053 g l,3,5,7-Tetramethyl-6-phenyl-2,4,8-trioxa-6- phosphaadamantane (0.181 mmol, 0.060 eq), and 2.82 g K3PO4 (13.3 mmol, 4.4 eq) were dissolved into 21 mL THF and 4.3 mL DI H2O. The reaction was stirred at 75°C overnight In the morning, the THF was removed. The resulting solid was extracted with DCM (50 mL). The DCM solution was then washed with DI water (3x50 mL). The DCM solution was dried with MgSO₄ and then filtered. Removal of solvent gave the crude product as brown solid. The impurities were washed out using acetone. Yield was calculated as 0.798 g (64%).

[0091] The1H NMR of Structure 3 was determined to be (400 MHz, Chloroform-d) 57.42 (s, 4H), 7.15 (s, 2H), 6.50 (q, J = 1.6 Hz, 2H), 3.25 (s, 4H), 2.99 (t, J = 7.3 Hz, 4H), 2.86 (t, J = 7.3 Hz, 4H), 2.12 (d, J = 1.5 Hz, 6H), 2.07 (p, J = 7.4 Hz, 4H).

[0092] Next, [4-[4-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6- methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]phenyl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-l- yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane as in Structure 4 was prepared.

[0093] 0.745 g 6-methyl-8-[4-(6-c-l,2,3,7-tetrahydro-s-indacen-4-yl)phenyl]-l,2,3,5-tetrahydro-s-indacene (1.49 mmol, 1 eq) and 0.980 g [dimethyl-(2, 3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl] trifluoromethanesulfonate (2.98 mmol, 2 eq) were dissolved into two separate 10 mL solutions of Et20. The lithium salt slurry was then added dropwise into the silane triflate solution. The reaction was allowed to stir overnight. In the morning, the solvent was removed. Product was extracted using dichloromethane (15 mL). Yield was calculated as 1.05 g (91%).

[0094] The1H NMR of Structure 4 was determined to be (400 MHz, CDC13) 5 7.46 (s, 4H), 7.28 (s, 2H), 6.67 - 6.60 (m, 2H). 3.66 (s. 2H), 3.30 (s, 2H), 3.08 - 2.79 (m, 12H), 2.21 (s, 6H), 2.06 (s, 6H), 2.02 (s, 6H), 1.87 (m, 12H), -0.24 (s, 6H), -0.27 (s, 6H).

[0095] Next, [4-[4-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methy 1- 1,2,3,7-tetrahydro-s-indacen-4-yl]phenyl] -2 -methyl- 1,5,6,7-tetrahy dro-s-indacen- 1 -yl]-dimethyl-(2.3.4.5-tetramethylcyclopenta-2,4-dien-l-yl)silane tetralithiate as in Structure 5 was prepared.Structure 5

[0096] 1.05 g [4-[4-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methy 1- 1,2,3,7-tetrahydro-s-indacen-4-yl]phenyl] -2 -methyl- 1,5,6,7-tetrahy dro-s-indacen- 1 -yl]-dimethyl-(2.3.4.5-tetramethylcyclopenta-2.4-dien-l-yl)silane (1.37 mmol. 1 eq) was dissolved into 20 mL Et20. 2.40 mL of 2.5M n-BuLi (6.01 mmol, 4.4eq) was then added dropwise into the solution. The solution was then stirred overnight. In the morning, the solution was filtered and washed with Et20 to isolate the product. The product was then dried in vacuo. Yield was calculated as 1.10 g (74%).

[0097] The 'H NMR of Structure 5 was determined to be (400 MHz, THF-d8) 5 7.55 (s, 4H), 7.46 (s, 2H), 5.98 (s, 2H), 3.03 - 2.68 (m, 12H), 2.39 (s, 6H), 2.13 (s, 12H), 1.93 (s, 12H), 0.61 (s, 12H).

[0098] Next, [4-[4-[7-[dimethyl-(2.3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl-1, 2, 3, 7-tetrahy dro-s-indacen-4-yl]phenyl]-2 -methyl-1, 5, 6, 7-tetrahy dro-s-indacen- 1-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane Bis(zirconium dichloride), catalyst II of Structure 6 was prepared.Structure 6

[0099] 0.206 g zirconium tetrachloride (0.886 mmol, 2 eq) was slurried into 10 mL Et20.0.500 g [4-[4-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl- l,2,3,7-tetrahydro-s-indacen-4-yl]phenyl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-l-yl]- dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane tetralithiate (0.443 mmol, 1 eq) was also slurried in a separate 10 mL Et20. The lithium salt was then added slowly into the ZrCL slurry. The reaction was then stirred overnight. In the morning, the solvent was removed. The residual solid was stirred in 20 mL pentane for 1 hour, filtered, and dried. The collected solid was then stirred in 20 mL dichloromethane for 1 hour and filtered to remove LiCl. The dichloromethane was then removed to give pure product. Yield was calculated as 0.214 g (44%).

[0100] The NMR of Structure 6 was determined to be (400 MHz, Methylene Chloride- d2) 5 7.74 - 7.59 (m, 4H), 7.40 (s, 2H), 6.81 (dd, J = 32.0, 3.2 Hz, 2H), 3.25 - 2.64 (m, 12H), 2.27 -2.21 (m, 6H), 2.05 (m, 6H), 1.96 (m, 6H), 1.93 (m, 6H), 1.90 (s, 6H), 1.22 (s, 6H), 1.09 (s, 6H).Synthesis of Catalyst 12

[0101] To begin synthesis of 12, a precursor chemical 6-methyl-4-[4-[4-(6-methyl-l, 2,3,7- tetrahydro-s-indacen-4-yl)phenyl]phenyl]-l,2,3,5-tetrahydro-s-indacene of Structure 7 was prepared.Structure 7

[0102] In a 50 mL bomb flask, 1.13 g 8-bromo-6-methyl-1.2.3.5-tetrahydro-s-indacene (4.55 mmol, 2.2 eq), 0.5 g 4,4’-biphenyldiboronic acid (2.07 mmol, 1 eq), 0.047 g Pd(dba)2 (0.052 mmol, 0.025 eq), 0.036 g l,3,5,7-Tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (0.124 mmol, 0.060 eq), and 1.93 g K3PO4 (9.10 mmol, 4.4 eq) were dissolved into 21 mL THF and 4.3 mL DI H2O. The reaction was stirred at 75°C overnight. In the morning, the THF was removed. The resulting solid was extracted with diethyl ether (50 mL). The diethyl ether solution was then washed with DI water (3x50 mL). The diethyl ether solution was dried with MgSO₄ and then filtered. Removal of solvent gave the crude product as brown solid. The impurities were w ashed out using acetone. Yield was calculated to be 0.606 g (60%).

[0103] The ’H NMR of Structure 7 was determined to be (400 MHz, Chloroform-d) 5 7.75 - 7.71 (m, 4H), 7.51 - 7.46 (m, 4H), 7.16 (s, 2H), 6.50 (q, J = 1.5 Hz, 2H), 3.24 (s, 4H), 3.00 (t, J = 7.4 Hz, 4H), 2.85 (t, J = 7.3 Hz, 4H), 2.12 (d, J = 1.5 Hz, 6H), 2.07 (q, J = 7.4 Hz, 4H).

[0104] Next, 6-methyl-4-[4-[4-(6-methyl- 1,2,3, 7-tetrahydro-s-indacen-4-yl)phenyl]phenyl]-l,2,3,5-tetrahydro-s-indacene dilithiate as in Structure 8 was prepared.Structure 8

[0105] In a 20 mL scintillation vial, 0.460 g 6-methyl-4-[4-[4-(6-methyl-l, 2,3,7-tetrahydro-s-indacen-4-yl)phenyl]phenyl]-l,2,3,5-tetrahydro-s-indacene (0.937 mmol, 1 eq) was dissolved into 20 mL Et20. 0.825 mL of 2.5M w-BuLi (2.06 mmol, 2.2eq) was then added dropwise. The reaction was then vigorously stirred overnight. In the morning, the Et20 was removed in vacuo. The orange residual solid was stirred in pentane for 1 hour. The product was then isolated by filtration and washed with 2 mL pentane. The product was dried in vacuo. Yield was calculated to be 0.235 g (50%).

[0106] The1H NMR of Structure 8 was determined to be (400 MHz, THF-d8) 5 7.77 - 7.74 (m, 4H), 7.74 - 7.70 (m, 4H), 7.12 (s, 2H), 5.85 (d, J = 2.1 Hz, 2H), 5.77 (d, J = 2.2 Hz. 2H), 2.98 - 2.91 (m, 8H), 2.41 - 2.32 (m, 6H), 1.98 (q, J = 6.9 Hz, 4H).

[0107] Next [4-[4-[4-[7-[dimethyl-(2.3.4.5-tetramethylcyclopenta-2.4-dien-l-yl)silyl]-6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]phenyl]phenyl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane as in Structure 9 was prepared.Structure 9

[0108] 0.1 g 6-methyl-4-[4-[4-(6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl)phenyl]phenyl]-l,2,3,5-tetrahydro-s-indacene dilithiate (0.185 mmol. 1 eq) and 0.122 g [dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl] trifluoromethanesulfonate (0.371 mmol, 2 eq) were dissolved into two separate 10 mL solutions of Et20. The lithium salt slurry was then added dropwise into the silane triflate solution. The reaction was allowed to stir overnight In the morning, the solvent was removed. Product was extracted using di chloromethane (15 mL). Yield was calculated to be 0.150 g (96%).

[0109] The1H NMR of Structure 9 was determined to be (400 MHz, CDC13) 5 7.77 (d, J = 8.3 Hz, 4H), 7.65 (d, J = 8.3 Hz, 4H), 7.46 (s, 2H), 6.83 (s, 2H), 3.71 (s, 2H), 3.29 (s, 2H), 3.04 - 2.80 (m, 12H), 2.07 (d, J = 1.4 Hz, 6H), 2.02 (s, 8H). 1.95 (s, 8H), 1.86 (q, J = 1.4 Hz. 12H), -0.13 (d, J = 16.8 Hz, 12H).

[0110] Next, [4-[4-[4-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]phenyl]phenyl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane tetralithiate as in Structure 10 was prepared.Structure 10

[0111] 0.150 g [4-[4-[4-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]- 6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]phenyl]phenyl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane (0.177 mmol, 1 eq) was dissolved into 20 mL Et20. 0.283 mL of 2.5M n-BuLi (0.708 mmol, 4.4 eq) was then added dropwise into the solution. The solution was then stirred overnight. In the morning, the solvent was removed. The residual solid was stirred in pentane (20mL) and filtered to isolate the product. Product was then dried in vacuo. Yield was calculated to be 0.162 g (90%).

[0112] The1H NMR of Structure 10 was determined to be (400 MHz, THF-d8) 5 7.68 (s, Hz, 8H), 7.49 (s, 2H), 5.95 (s, 2H), 2.91 (t, J = 7.1 Hz, 8H), 2.41 (s, 6H), 2.16 (s, 12H), 2.08 (s, 6H), 2.05-2.00 (m, 4H), 1.96 (s, 12H), 0.64 (s, 12H).

[0113] Next, [4-[4-[4-[7-[dimethyl-(2.3.4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl-L2,3,7-tetrahydro-s-indacen-4-yl]phenyl]phenyl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-1 -yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l -yl)silane Bis(zirconium dichloride), Catalyst 12 of Structure 11 was prepared.Structure 11

[0114] 0.0875 g zirconium tetrachloride (0.375 mmol, 2 eq) was slurried into 10 mL Et20.0.500 g [4-[4-[4-[7-[dimethyl-(2.3.4.5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl-L2,3,7-tetrahydro-s-indacen-4-yl]phenyl]phenyl]-2-methyl-L5,6,7-tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane tetralithiate (0.188 mmol, 1 eq) was also slurried in a separate 10 mL Et20. The lithium salt was then added slowly into the ZrCl₄ slurry. The reaction was then stirred overnight. In the morning, the solvent was removed. The residual solid was stirred in 20 mL pentane for 1 hour, filtered, and dried. The collected solid was then stirred in 20 mL dichloromethane for 1 hour and filtered to remove LiCl. The dichloromethane was then removed to give pure product. Yield was calculated to be 0.113 g (52%).

[0115] The1H NMR of Structure 11 was determined to be (400 MHz, Methylene Chloride-d2) 5 7.83 - 7.79 (m, 4H), 7.71 (d, J = 7.9 Hz, 4H), 7.47 - 7.40 (m, 2H), 6.83 (s, 2H), 3.03 (t, J = 7.2 Hz, 4H), 3.01 - 2.93 (m, 4H), 2.88 (m, 4H), 2.29 (s, 6H), 2.08 (s, 6H), 2.00 (s, 6H), 1.97 (s, 6H), 1.94 (s, 6H), 1.26 (s, 6H), 1.13 (s, 6H).Catalyst 13

[0116] To begin synthesis of catalyst 13, 6-methyl-8-[3-(6-methyl-l,2,3,7-tetrahydro-s- indacen-4-yl)phenyl]-1.2.3.5-tetrahydro-s-indacene as in Structure 12 was prepared.Structure 12

[0117] In a 50 mL bomb flask, 1.65 g 8-bromo-6-methyl-l,2,3,5-tetrahydro-s-indacene (6.64 mmol, 2.2 eq), 0.5 g benzene- 1,3-diboronic acid (3.02 mmol, 1 eq), 0.043 g Pd(dba)₂ (0.075 mmol, 0.025 eq), 0.053 g 1,3,5,7-Tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (0.181 mmol. 0.060 eq), and 2.82 g K3PO4 (13.3 mmol, 4.4 eq) were dissolved into 21 mL THF and 4.3 mL DI H2O. The reaction was stirred at 75°C overnight. In the morning, the THF was removed. The resulting solid was extracted with DCM (50mL). The DCM solution was then washed with DI water (3x50 mL). The DCM solution was dried with MgSO₄ and then filtered. Removal of solvent gave the crude product as brown solid. The product was purified by column chromatography. Yield was calculated to be 0.586 g (47%).

[0118] The ’H NMR of Structure 12 was determined to be (400 MHz, Chloroform-d) 5 7.69 - 7.57 (m, 1H), 7.54 - 7.40 (m, 2H), 7.40 - 7.29 (m, 3H), 7.14 (d, J = 5.0 Hz, 2H), 6.48 (q, J = 1.6 Hz, 2H), 2.97 (t, J = 7.4 Hz, 4H), 2.82 (t, J = 7.3 Hz, 4H), 2.09 (t, J = 2.1 Hz, 6H), 2.08 - 2.00 (m, 4H).

[0119] Next 6-methyl-8-[3-(6-methyl-L2,3,7-tetrahydro-s-indacen-4-yl)phenyl]-l,2,3,5- tetrahydro-s-indacene dilithiate of Structure 13 was prepared.Structure 13

[0120] In a 20 mL scintillation vial, 0.586 g 6-methyl-8-[3-(6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl)phenyl]-l,2,3,5-tetrahydro-s-indacene (1.41 mmol, 1 eq) was dissolved into 20 mL Et20. 1.24 mL of 2.5M n-BuLi (3.11 mmol, 2.2 eq) was then added dropwise. The reaction was then vigorously stirred overnight. In the morning, the Et20 was removed in vacuo. The orange residual solid was stirred in pentane for 1 hour. The product was then isolated by filtration and washed with 2 mL pentane. The product was dried in vacuo. Yield was calculated to be 0.603 g (100%).

[0121] The 'H NMR of Structure 13 was determined to be (400 MHz, THF-d8) 5 7.96 (m, 1H), 7.68 - 7.47 (m, 1H), 7.43 - 7.35 (m, 2H). 7.31 (dd, J = 8.5, 6.4 Hz, 1H), 7.05 (t, J = 2.5 Hz, 2H), 5.76 (d, J = 2.1 Hz, 2H), 5.68 (d, J = 2.2 Hz, 2H), 3.01 - 2.84 (m, 8H), 2.28 (s, 6H), 1.94 (p, J = 7.0 Hz, 4H).

[0122] Next, [4-[3-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]phenyl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane of Structure 14 was prepared.Structure 14

[0123] 0.300 g 6-methyl-8-[3-(6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl)phenyl]- 1,2,3,5-tetrahydro-s-indacene dilithiate (0.647 mmol, 1 eq) and 0.425 g [dimethyl-(2, 3,4,5- tetramethylcyclopenta-2,4-dien-l-yl)silyl] trifluoromethanesulfonate (1.29 mmol, 2 eq) were dissolved into two separate 10 mL solutions of Et20. The lithium salt slurry was then added dropwise into the silane triflate solution. The reaction was allowed to stir overnight. In the morning, the solvent was removed. Product was extracted using pentane (15 mL) as a mixture of isomers. Yield was calculated to be 0.499 g (100%).

[0124] The1H NMR of Structure 14 was determined to be (400 MHz, Chloroform-d) 5 7.75 - 7.55 (m, 1H), 7.55 - 7.44 (m, 1H), 7.44 - 7.39 (m, 1H), 7.39 - 7.27 (m, 3H), 6.66 - 6.35 (m, 2H), 3.64 (s, 2H), 3.28 (s, 2H), 3.04 - 2.73 (m, 8H), 2.18 (m, 6H), 2.04 (s, 6H), 2.00 (s, 6H), 1.85 (m, 12H), -0.28 (d, J = 9.8 Hz, 12H).

[0125] Next, [4-[3-[7-[dimethyl-(2.3.4.5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6- methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]phenyl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-l- yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane tetralithiate of Structure 15 was prepared.Structure 15

[0126] 0.511 g [4-[3-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6- methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]phenyl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-l- yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane (0.662 mmol, 1 eq) was dissolved into 20 mL Et20. 1.17 mL of 2.5M n-BuLi (2.91 mmol, 4.4 eq) was then added dropwise into the solution. The solution was then stirred overnight. In the morning, the solution was filtered and washed with Et20 to isolate the products a mixture of isomers. Product was then dried in vacuo. Yield was calculated to be 0.599 g (89%).

[0127] The 'H NMR of Structure 15 was determined to be (400 MHz, THF-d8) S 7.90 (m, 1H), 7.61 - 7.49 (m, 1H), 7.43 (d, J = 7.7 Hz, 1H), 7.38 (d, J = 7.5 Hz, 1H), 7.30 (d, J = 7.8 Hz, 1H), 5.93 (m, 2H), 2.90 (m, 8H). 2.34 (m. 6H), 2.11 (m, 9H), 2.03 - 1.84 (m, 13H), 1.76 (m, 6H), 0.41 (m, 12H).

[0128] Next, [4-[3-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl-1,2,3,7-tetrahydro-s-indacen-4-yl]phenyl] -2-methyl-l,5,6,7-tetrahy dro-s-indacen- 1 -yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane Bis(zirconium dichloride), Catalyst 13 of structure 16 was prepared.Structure 16

[0129] 0.275 g zirconium tetrachloride (1.18 mmol, 2 eq) was slurried into 10 mL Et₂O.0.500 g [4-[3-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]phenyl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4.5-tetramethylcyclopenta-2,4-dien-l-yl)silane tetralithiate (0.589 mmol, 1 eq) was also slurried in a separate 10 mL Et20. The lithium salt was then added slowly into the ZrCl₄ slurry. The reaction was then stirred overnight. In the morning, the solvent was removed. The residual solid was stirred in 20 mL pentane for 1 hour, filtered, and dried. The collected solid was then stirred in 20 mL dichloromethane for 1 hour and filtered to remove LiCl. The dichloromethane was then removed to give pure product. Yield was calculated to be 0.460 g (72%).

[0130] The1H NMR of Structure 16 was determined to be (400 MHz, Methylene Chloride-d2) δ 8.03 - 7.26 (m, 6H). 6.94 - 6.59 (m. 2H), 3.88 - 2.60 (m, 12H). 2.28 - 2.23 (m. 6H), 2.07 (m, 6H), 1.99 - 1.95 (m, 12H), 1.91 (m, 6H), 1.24 (s, 6H), 1.12 (s, 6H).Catalyst 14

[0131] To begin synthesis of catalyst 14, 9,9-dimethyl-l,8-bis(6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl)lluorene of Structure 17 was prepared.Structure 17

[0132] In a 50 mL bomb flask, 0.972 g 8-bromo-6-methyl-l,2,3,5-tetrahydro-s-indacene (3.90 mmol, 2.2 eq), 0.5 g 2,7-fluorenyldiboronic acid (1.77 mmol, 1 eq), 0.041 g Pd(dba)₂ (0.044 mmol, 0.025 eq), 0.031 g 1,3,5,7-Tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (0.106 mmol, 0.060 eq), and 1.66 g K3PO4 (7.80 mmol, 4.4 eq) were dissolved into 21 mL THF and 4.3 mL DI H2O. The reaction was stirred at 75°C overnight In the morning, the THF was removed. The resulting solid was extracted with diethyl ether (50 mL). The diethyl ether solution was then washed with DI water (3x50 mL). The diethyl ether solution was dried with MgSO₄ and then filtered. Removal of solvent gave the crude product as brown solid. The impurities were washed out using acetone. Yield was calculated to be 0.260 g (28%).

[0133] The 'H NMR of Structure 17 was determined to be (400 MHz, Chloroform-d) 5 7.79 (d, J = 7.7 Hz, 2H), 7.47 (d, J = 1.5 Hz, 2H), 7.38 (dd, J = 7.8, 1.5 Hz, 2H), 7.26 (s, 1H), 7.15 (s, 2H), 6.50 (d, J = 1.5 Hz, 2H), 3.23 (s, 6H), 2.99 (t, J = 7.4 Hz, 4H), 2.84 (t, J = 7.3 Hz, 4H), 2.11 (d, J = 1.5 Hz, 6H), 2.06 (q, J = 7.4 Hz, 4H), 1.54 (s, 6H).

[0134] Next, 9,9-dimethyl-l,8-bis(6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl)fluorene dilithiate of Structure 18 was prepared.Structure 18

[0135] In a 20 mL scintillation vial, 0.260 g 9,9-dimethyl-l,8-bis(6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl)fluorene (0.490 mmol, 1 eq) was dissolved into 20 mL Et20.0.431 mL of 2.5M n-BuLi (1.08 mmol, 2.2 eq) was then added dropwise. The reaction was then vigorously stirred overnight. In the morning, the Et20 was removed in vacuo. The orangeresidual solid was stirred in pentane for 1 hour. The product was then isolated by filtration and washed with 2 mL pentane. The product was dried in vacuo. Yield was calculated to be 0.190 g (72%).

[0136] The 'H NMR of Structure 18 was determined to be (400 MHz, THF-d8) 5 7.82 - 7.77 (m, 2H), 7.69 (d, J = 7.8 Hz, 2H), 7.61 (dd, J = 7.8, 1.5 Hz, 2H), 7.09 (s, 2H), 5.85 (d, J = 2.2 Hz, 2H), 5.73 (d, J = 2.2 Hz, 2H), 2.93 (dt, J = 17.4, 7.0 Hz, 8H), 2.34 (s, 6H), 1.94 (p, J = 7.1 Hz. 4H), 1.57 (s, 6H).

[0137] Next, [4-[8-[7-[dimethyl-(2.3.4.5-tetramethylcyclopenta-2.4-dien-l-yl)silyl]-6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]-9,9-dimethyl-fluoren-l-yl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane of Structure 19 was prepared.Structure 19

[0138] 0.190 g 9,9-dimethyl-l,8-bis(6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl)fluorene dilithiate (0.351 mmol, 1 eq) and 0.230 g [dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl] trifluoromethanesulfonate (0.701 mmol, 2 eq) were dissolved into two separate 10 mL solutions of Et20. The lithium salt slurry was then added dropwise into the silane triflate solution. The reaction was allowed to stir overnight. In the morning, the solvent was removed. Product was extracted using pentane (15 mL). Yield was calculated to be 0.291 g (94%).

[0139] The1H NMR of Structure 19 was determined to be (400 MHz, CDC13) 5 7.80 (d, J = 7.8 Hz, 2H), 7.49 (s, 2H), 7.39 (dd, J = 7.7, 1.5 Hz, 2H), 7.29 (s, 2H), 6.58 (d, J = 1.8 Hz, 2H), 3.30 (s, 2H), 3.07 - 2.80 (m, 12H), 2.20 (d, J = 1.4 Hz, 6H), 2.07 (s. 6H), 2.02 (s, 6H), 1.96 (s, 6H). 1.88 (d, J = 1.4 Hz, 6H), 1.86 (t, J = 1.3 Hz. 6H), -0.22 (s, 6H), -0.25 (s, 6H).

[0140] Next, [4-[8-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl-1, 2,3, 7-tetrahy dro-s-indacen-4-yl]-9,9-dimethyl-fluoren-l-yl]-2-methyl-l, 5,6,7-tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane tetralithiate of Structure 20 was prepared.SiStructure 20

[0141] 0.291 g [4-[8-[7-[dimethyl-(2.3.4.5-tetramethylcyclopenta-2.4-dien-l-yl)silyl]-6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]-9,9-dimethyl-fluoren-l-yl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane (0.328 mmol, 1 eq) was dissolved into 20 mL Et20. 0.577 mL of 2.5M n-BuLi (1.44 mmol, 4.4 eq) was then added dropwise into the solution. The solution was then stirred overnight. In the morning, the solvent was removed. The residual solid was stirred in pentane (20 mL) and filtered to isolate the product. Product was then dried in vacuo. Yield was calculated to be 0.314 g (90%).

[0142] The 'H NMR of Structure 20 was determined to be (400 MHz, THF-d8) 5 7.70 (s, 2H), 7.67 (d, J = 7.6 Hz. 2H), 7.56 - 7.50 (m, 2H), 7.46 (s, 2H), 5.94 (s. 2H), 2.89 (q, J = 7.0 Hz, 8H), 2.36 (s, 6H), 2.12 (s, 6H), 1.92 (s, 18H), 1.53 (s, 6H), 1.31 (m, 4H), 0.60 (s, 12H).

[0143] Next, [4-[8-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]-9,9-dimethyl-fluoren-l-yl]-2-methyl-L5,6,7-tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane Bis(zirconium dichloride), catalyst 14 of Structure 21 was prepared.Structure 21

[0144] 0.138 g zirconium tetrachloride (0.592 mmol, 2 eq) was slurried into 10 mL Et20.0.314 g [4-[8-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]-9,9-dimethyl-fluoren-l-yl]-2-methyl-L5,6,7-tetrahydro-s-indacen-1 -yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien- 1 -yl)silane tetralithiate (0.296 mmol, 1 eq) was also slurried in a separate 10 mL Et20. The lithium salt was then added slowly into the ZrCL slurry. The reaction was then stirred overnight. In the morning, the solvent was removed. The residual solid was stirred in 20 mL pentane for 1 hour, filtered, and dried. The collected solid was then stirred in 20 mL dichloromethane for 1 hour and filtered to remove LiCl. The dichloromethane was then removed to give pure product. Yield was determined to be 0.243 g (68%).

[0145] The1H NMR of Structure 21 was determined to be (400 MHz, Methylene Chloride-d2) 5 7.83 (d. J = 7.7 Hz, 2H), 7.78 (s, 2H), 7.64 - 7.51 (b, 2H), 7.42 - 7.36 (b, 2H), 6.79 (s, 2H), 3.44 - 2.59 (m, 12H), 2.24 (s, 6H), 2.05 (s, 6H), 1.98 (s, 6H), 1.94 (s, 6H), 1.92 (s, 6H), 1.55 (t, J = 23.7 Hz, 6H), 1.22 (s, 6H), 1.10 (s, 6H).Catalyst 15

[0146] To begin synthesis of catalyst 15, 6-methyl-8-[4-(6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl)-l-naphthyl]-l,2,3,5-tetrahydro-s-indacene of Structure 22 was prepared.Structure 22

[0147] In a 50 mL bomb flask, 1.27 g 8-bromo-6-methyl-l,2,3,5-tetrahydro-s-indacene (5.10 mmol. 2.2 eq), 0.5 g naphthalene-1.4-diboronic acid (2.32 mmol. 1 eq), 0.033 g Pd(dba)2 (0.058 mmol, 0.025 eq), 0.041 g l,3,5,7-Tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (0.139 mmol, 0.060 eq), and 2.16 g K3PO4 (10.2 mmol, 4.4 eq) were dissolved into 21 mL THF and 4.3 mL DI H2O. The reaction was stirred at 75°C overnight. In the morning, the THF was removed. The resulting solid was extracted with DCM (50mL). The DCM solution was then washed with DI water (3x50mL). The DCM solution was dried with MgSO4and then fdtered. Removal of solvent gave the crude product as brow n solid. The impurities w ere washed out using acetone. Yield w as calculated to be 0.442 g (41%).

[0148] The1H NMR of Structure 22 was determined to be (400 MHz, Chloroform-d) 5 7.90 (ddd. J = 17.6. 8.4, 1.1 Hz, 4H), 7.57 - 7.31 (m, 12H). 7.22 (s. 2H), 6.52 (q, J = 1.5 Hz, 2H), 3.01 (dd, J = 15.2, 7.8 Hz, 12H), 2.87 - 2.75 (m, 2H), 2.60 (dt, J = 15.2, 7.4 Hz, 2H), 2.45 (dt, J = 15.6, 7.3 Hz, 2H), 2.02 (d, J = 1.5 Hz, 6H).

[0149] Next, 6-methyl-8-[4-(6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl)-l-naphthyl]- 1,2,3,5-tetrahydro-s-indacene dilithiate of Structure 23 was prepared.Structure 23

[0150] In a 20 mL scintillation vial, 0.442 g 6-methyl-8-[4-(6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl)-l-naphthyl]-l,2,3,5-tetrahydro-s-indacene (0.951 mmol, 1 eq) was dissolved into 20 mL Et20. 0.837 mL of 2.5M n-BuLi (2.09 mmol, 2.2 eq) was then added dropwise. The reaction was then vigorously stirred overnight. In the morning, the Et20 was removed in vacuo. The orange residual solid was stirred in pentane for 1 hour. The product was then isolated by filtration and washed with 2 mL pentane. The product was dried in vacuo. Yield was calculated to be 0.275 g (61%).

[0151] The 'H NMR of Structure 23 was determined to be (400 MHz, THF-d8) 6 7.88 - 7.65 (m. 4H), 7.53 - 7.29 (m, 4H), 7.22 - 7.04 (m, 4H). 5.73 (m. 2H), 5.39 - 5.12 (m, 2H), 3.06 - 2.86 (m, 4H), 2.67 - 2.38 (m, 4H), 2.24 (m, 6H), 1.90 (m, 4H).

[0152] Next, [4-[4-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methy 1-1,2,3,7-tetrahydro-s-indacen-4-yl]- 1 -naphthyl] -2 -methyl- 1,5,6,7 -tetrahy dro-s-indacen-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane of Structure 24 was prepared.Structure 24

[0153] 0.280 g 6-methyl-8-[4-(6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl)-l-naphthyl]- 1,2,3,5-tetrahydro-s-indacene dilithiate (0.578 mmol, 1 eq) and 0.380 g [dimethyl-(2, 3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl] trifluoromethanesulfonate (1.16 mmol, 2 eq) were dissolved into two separate 10 mL solutions of Et20. The lithium salt slurry was then added dropwise into the silane triflate solution. The reaction was allowed to stir overnight. In the morning, the solvent was removed. Product was extracted using di chloromethane (15 mL). Yield was calculated to be 0.472 g (100%).

[0154] The1H NMR of Structure 24 was determined to be (400 MHz, CDC13) 5 7.92 (dd, J = 17.8, 8.1 Hz, 2H), 7.62 - 7.32 (m, 8H), 6.34 - 5.89 (m, 2H), 3.72 (m, 2H), 3.37 (m, 2H), 3.05 (m, 4H), 2.92 - 2.45 (m, 4H), 2.17 - 1.80 (m, 34H), -0.18 - -0.30 (m, 12H).

[0155] Next, [4-[4-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methy 1- 1,2,3, 7-tetrahy dro-s-indacen-4-y 1]- 1 -naphthyl] -2 -methyl- 1,5,6, 7-tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane tetralithiate of Structure 25 was prepared.Structure 25

[0156] 0.472 g [4-[4-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl-1,2,3,7-tetrahydro-s-indacen-4-yl]- 1 -naphthyl] -2-methyl- 1,5,6,7 -tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane (0.575 mmol, 1 eq) was dissolved into 20 mL Et20. 1.01 mL of 2.5M n-BuLi (2.53 mmol, 4.4 eq) was then added dropwise into the solution. The solution was then stirred overnight. In the morning, the solution was filtered and washed with Et20 to isolate the product. Product was then dried in vacuo. Yield was determined to be 0.512 g (83%).

[0157] The1H NMR of Structure 25 was determined to be (400 MHz, THF-d8) 6 8.02 - 6.97 (m, 10H), 3.15 - 2.25 (m, 12H), 2.25 - 1.76 (m, 30H), 0.39 - -0.47 (m, 12H).

[0158] Next, [4-[4-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silylJ-6-methyl-1,2,3, 7-tetrahy dro-s-indacen-4-yl]- 1 -naphthyl] -2-methyl- 1,5,6, 7-tetrahydro-s-indacen-1 -yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l -yl)silane Bis(zirconium dichloride), Catalyst 15 of Structure 26 was prepared.Structure 26

[0159] 0.131 g zirconium tetrachloride (0.562 mmol, 2 eq) was slurried into 10 mL Et20.0.500 g [4-[4-[7-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-6-methyl-l,2,3,7-tetrahydro-s-indacen-4-yl]-l-naphthyl]-2-methyl-l,5,6,7-tetrahydro-s-indacen-l-yl]-dimethyl-(2,3,4.5-tetramethylcyclopenta-2.4-dien-l-yl)silane tetralithiate (0.281 mmol, 1 eq) was also slurried in a separate 10 mL Et20. The lithium salt was then added slowly into the ZrCl4 slurry. The reaction was then stirred overnight. In the morning, the solvent was removed. The residual solid was stirred in 20 mL pentane for 1 hour, filtered, and dried. The collected solid was then stirred in 20 mL dichloromethane for 1 hour and filtered to remove LiCl. The dichloromethane was then removed to give pure product. Yield was calculated to be 0.102 g (32%).

[0160] TheNMR of Structure 26 was determined to be (400 MHz, Methylene Chloride-d2) 5 8.77 - 7.77 (m, 2H), 7.74 - 7.04 (m, 7H), 6.98 - 6.19 (m. 1H), 3.29 - 2.40 (m, 8H), 2.36 - 1.50 (m, 34H). 1.28 - 1.14 (m, 6H). 1.09 (m, 6H).Catalyst 17

[0161] To begin synthesis of catalyst 17, l,l'-bis(6-methyl-l,2,3,5-tetrahydro-s-indacene)ferrocene as in Structure 27 was prepared.Structure 27

[0162] In a 50 mL bomb flask, 1.00 g 8-bromo-6-methyl-l,2,3,5-tetrahydro-s-indacene (4.02 mmol, 2.2 eq), 0.5 g ferrocene- l,r-diboronic acid (1.83 mmol. leq). 0.026 g Pd(dba)2 (0.046 mmol, 0.025 eq), 0.032 g 1,3,5, 7-Tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (0.110 mmol, 0.060 eq), and 1.71 g K3PO4 (8.04 mmol, 4.4 eq) were dissolved into 21 mL THF and 4.3 mL DI H2O. The reaction was stirred at 75°C overnight. In the morning, the THF was removed. The resulting solid was extracted with DCM (50 mL). The DCM solution was then washed with DI water (3x50 mL). The DCM solution was dried with MgSO4and then fdtered. Removal of solvent gave the crude product as brown solid. The product was purified by column chromatography. Yield was calculated to be 0.547 g (57%).

[0163] The 'l l NMR of Structure 27 was determined to be (400 MHz, Chloroform-d) 6 7.68 - 7.57 (m, 1H), 7.53 - 7.30 (m, 7H), 7.14 (m, 2H), 6.48 (q, J = 1.6 Hz, 2H), 3.21 (s, 4H), 2.97 (t, J = 7.4 Hz, 4H), 2.82 (t, J = 7.3 Hz, 4H), 2.09 (t, J = 2.1 Hz, 6H), 2.08 - 1.99 (m, 4H).

[0164] Next, l,r-bis(6-methyl-l,2,3,5-tetrahydro-s-indacene)ferrocene dilithiate of Structure 28 w as prepared.Structure 28

[0165] In a 20 mL scintillation vial, 0.547 g l,l'-bis(6-methyl-l,2,3,5-tetrahydro-s-indacene)ferrocene (1.05 mmol, 1 eq) was dissolved into 20 mL Et20. 0.922 mL of 2.5M / r-BuLi (2.30 mmol, 2.2 eq) was then added dropwise. The reaction was then vigorously stirred overnight. In the morning, the Et20 was removed in vacuo. The orange residual solid was stirred in pentane for 1 hour. The product was then isolated by filtration and washed with 2 mL pentane and 2 mL Et20. The product was dried in vacuo. Yield was determined to be 0.512 g (92%).

[0166] The1H NMR of Structure 28 was determined to be (400 MHz, THF-d8) 5 7.96 (m, 1H), 7.70 - 7.22 (m, 7H), 7.05 (m, 2H), 5.77 (m, 2H), 5.69 (m, 2H), 2.97 - 2.83 (m, 8H), 2.28 (s, 6H), 1.93 (p, J = 6.9 Hz, 4H).

[0167] Next, LE-bis(dimethyl(2 -methyl -4-(l,5,6,7-tetrahydro-s-indacen-l-yl))(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl)ferrocene of Structure 29 was prepared.Structure 29

[0168] 0.547 g l,l'-bis(6-methyl-l,2,3,5-tetrahydro-s-indacene)ferrocene dilithiate (0.958 mmol, 1 eq) and 0.629 g [dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl] trifluoromethanesulfonate (1.92 mmol, 2 eq) were dissolved into two separate 10 mL solutions ofEt2O. The lithium salt slurry was then added dropwise into the silane triflate solution. The reaction was allowed to stir overnight. In the morning, the solvent was removed. Product was extracted using pentane (15 mL). Yield was calculated to be 0.571 g (68%).

[0169] The1H NMR of Structure 29 was determined to be (400 MHz, CDC13) 5 7.75 - 7.31 (m, 8H), 7.28 (m, 2H), 6.69 - 6.30 (m, 2H), 3.64 (s, 2H), 3.29 (s, 2H), 3.08 - 2.71 (m, 8H), 2.19 (d, J = 2.1 Hz, 6H), 2.13 - 2.06 (m, 4H), 2.05 (s, 6H), 2.00 (s, 6H), 1.87 (s, 5H), 1.86 (s, 6H), -0.27 (d, J = 10.6 Hz, 12H).

[0170] Next, 1.1 '-bis(dimethyl(2 -methyl -4-(l, 5,6, 7-tetrahydro-s-indacen-l-yl))(2, 3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl)ferrocene tetralithiate of Structure 30 was prepared.Structure 30

[0171] 5.71 g l,l’-bis(dimethyl(2 -methyl -4-(l,5,6,7-tetrahydro-s-indacen-l-yl))(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl)ferrocene (0.648 mmol, 1 eq) was dissolved into 20 mL Et20. 1.14 mL of 2.5M «-BuLi (2.85 mmol, 4.4 eq) was then added dropwise into the solution. The solution was then stirred overnight. In the morning, the solution was fdtered and washed with Et20 to isolate the product. Product was then dried in vacuo. Yield was calculated to be 0.643 g (88%).

[0172] The1H NMR of Structure 30 was determined to be (400 MHz, THF-d8) 5 8.23 - 6.62 (m, 10H), 5.90 (d, J = 13.5 Hz, 2H), 2.87 (m, 12H), 2.32 (s, 6H), 2.11 (s, 12H), 1.92 (d, J = 2.9 Hz, 12H). 0.58 (s, 12H).

[0173] Next, l,r-bis(dimethyl(2 -methyl -4-(l,5,6,7-tetrahydro-s-indacen-l-yl))(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl)ferrocene Bis(zirconium dichloride), Catalyst 17 of Structure 31 was prepared.Structure 31

[0174] 0.124 g zirconium tetrachloride (0.533 mmol, 2 eq) was slurried into 10 mL Et20.0.300 g l,r-bis(dimethyl(2-methyl -4-(l,5,6,7-tetrahydro-s-indacen-l-yl))(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl)ferrocene tetralithiate (0.267 mmol, 1 eq) was also slurried in a separate 10 mL Et20. The lithium salt was then added slowly into the ZrCl4slurry. The reaction was then stirred overnight. In the morning, the solvent was removed. The residual solid was stirred in 20 mL pentane for 1 hour, filtered, and dried. The collected solid was then stirred in 20 mL dichloromethane for 1 hour and filtered to remove LiCl. The dichloromethane was then removed to give pure product. Yield was calculated to be 0.208 g (65%).

[0175] TheNMR of Structure 31 was determined to be (400 MHz, Methylene Chloride-d2) 5 8.11 - 7.07 (m, 10H), 6.99 - 6.41 (m, 2H), 3.66 - 2.57 (m. 12H), 2.27 - 2.19 (m, 6H), 2.03 (m, 6H), 1.99 - 1.94 (m, 6H), 1.94 - 1.91 (m, 6H), 1.89 (m, 6H), 1.21 (m, 6H), 1.08 (m, 6H).Catalyst C2

[0176] To begin synthesis of catalyst C2, 2-methyl-4-[4-[4-(2-methyl-3H-inden-4-yl)phenyl]phenyl]-lH-indene of Structure 32 was prepared.Structure 32

[0177] In a 50 mL bomb flask, 0.951 g 4-bromo-2-methyl-lH-indene (4.55 mmol, 2.2 eq), 0.5 g 4,4'-biphenyldiboronic acid (2.07 mmol, 1 eq), 0.047 g Pd(dba)2 (0.052 mmol, 0.025 eq), 0.036 g l,3,5,7-Tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (0.124 mmol, 0.060 eq), and 1.93 g K3PO4 (9.10 mmol, 4.4 eq) were dissolved into 21 mL THF and 4.3 mL DI H2O. The reaction was stirred at 75°C overnight. In the morning, the THF was removed. The resulting solid was extracted with diethyl ether (50 mL). The diethyl ether solution was then washed with DI water (3x50 mL). The diethyl ether solution was dried with MgSO₄ and then filtered. Removal of solvent gave the crude product as brown solid. The impurities were washed out using acetone. Yield was calculated to be 0.267 g (32%).

[0178] The1H NMR of Structure 23 was determined to be (400 MHz, Chloroform-d) 6 7.75 - 7.71 (m, 4H), 7.64 (d, J = 8.2 Hz. 4H), 7.33 (d, J = 7.5 Hz, 2H). 7.26 (d, J = 12.6 Hz, 2H), 7.20 (dd, J = 7.5, 1.2 Hz, 2H), 6.56 (d, J = 1.6 Hz, 2H), 3.45 (s, 4H), 2.16 (d, J = 2.1 Hz, 6H).

[0179] Next, 2-methyl-4-[4-[4-(2-methyl-3H-inden-4-yl)phenyl]phenyl]-lH-indene dilithiate of Structure 33 was prepared.Structure 33

[0180] In a 20 mL scintillation vial, 0.267 g 2-methyl-4-[4-[4-(2-methyl-3H-inden-4-yl)phenyl]phenyl]-lH-indene (0.650 mmol, 1 eq) was dissolved into 20 mL Et20. 0.572 mL of 2.5M n-BuLi (1.43 mmol, 2.2 eq) was then added dropwise. The reaction was then vigorously stirred overnight. In the morning, the Et20 was removed in vacuo. The orange residual solid was stirred in pentane for 1 hour. The product was then isolated by filtration and washed with 2 mL pentane. The product was dried in vacuo. Yield was calculated to be 0.230 g (84%).

[0181] The1H NMR of Structure 33 was determined to be (400 MHz, THF-d8) 5 7.72 - 7.60 (m, 4H), 7.47 - 7.37 (m, 4H), 6.95 (dt, J = 7.8, 1.0 Hz, 2H), 6.37 (dd, J = 6.9, 1.1 Hz, 2H), 6.27 (dd, J = 7.9, 6.9 Hz, 2H), 5.87 (d, J = 2.0 Hz, 2H), 5.64 - 5.54 (m, 2H), 2.15 (s, 6H).

[0182] Next, [4-[4-[4-[l-[dimethyl-(2.3.4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-2-methyl-lH-inden-4-yl]phenyl]phenyl]-2-methyl-lH-inden-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane of Structure 34 was prepared.Structure 34

[0184] 0.311 g 2-methyl-4-[4-[4-(2-methyl-3H-inden-4-yl)phenyl]phenyl]-lH-indene dilithiate (0.545 mmol, 1 eq) and 0.358 g [dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl] trifluoromethanesulfonate (1.09 mmol, 2 eq) were dissolved into two separate 10 mL solutions of Et20. The lithium salt slurry was then added dropwise into the silane triflate solution. The reaction was allowed to stir overnight. In the morning, the solvent was removed. Product was extracted using dichloromethane (15 mL). Yield was calculated to be 0.418 g (100%).

[0185] TheNMR of Structure 34 was determined to be (400 MHz, CDC13) 5 7.76 (d, J = 8.2 Hz. 4H), 7.66 - 7.64 (m, 4H), 7.41 (d, J = 7.5 Hz, 2H). 7.31 (d, J = 7.6 Hz. 2H), 7.19 (t, J = 7.6 Hz, 2H), 6.85 (s, 2H), 2.27 (d, J = 1.4 Hz, 6H), 2.04 (s, 6H), 2.01 (s, 6H), 1.96 (d, J = 2.5 Hz, 6H), 1.88 - 1.86 (m, 6H), 1.86 (s, 6H), 1.81 (s, 6H), -0.23 (s, 6H), -0.26 (s, 6H).

[0186] Next, [4-[4-[4-[l-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-2-methyl-lH-inden-4-yl]phenyl]phenyl]-2-methyl-lH-inden-l -yl]-dimethyl-(2, 3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane tetralithiate of Structure 35 was prepared.Structure 35

[0187] 0.440 g [4-[4-[4-[l-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]- 2-methyl-lH-inden-4-yl]phenyl]phenyl]-2-methyl-lH-inden-l-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane (0.574 mmol, 1 eq) was dissolved into 20 mL Et20.1.01 mL of 2.5M n-BuLi (2.52 mmol, 4.4 eq) was then added dropwise into the solution. The solution was then stirred overnight. In the morning, the solids were filtered and washed with Et20 to isolate the product. Product was then dried in vacuo. Yield was calculated to be 0.511 g (82%).

[0188] The1H NMR of Structure 35 was determined to be (400 MHz, THF-d8) 5 7.83 (d, J = 8.1 Hz, 4H), 7.64 (d, J = 8.0 Hz, 4H), 7.57 (s, 3H), 6.59 (d, J = 6.6 Hz, 2H), 6.52 (d, J = 7.8 Hz, 2H), 6.21 (s, 2H), 2.46 (s, 6H), 2.13 (s, 12H), 1.91 (s, 12H), 0.61 (s, 12H).

[0189] Next, [4-[4-[4-[l-[dimethyl-(2.3.4.5-tetramethylcyclopenta-2,4-dien-l-yl)silyl]-2-methyl-lH-inden-4-yl]phenyl]phenyl]-2-methyl-lH-inden-l -yl]-dimethyl-(2, 3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane Bis(zirconium dichloride), Catalyst C2 of Structure 36 was prepared.Structure 36

[0190] 0.107 g zirconium tetrachloride (0.460 mmol, 2 eq) was slurried into 10 mL Et20.0.250 g [4-[4-[4-[1-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl]-2-methyl-1H-inden-4-yl]phenyl]phenyl]-2-methyl-1H-inden-1-yl]-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane tetralithiate (0.230 mmol, 1 eq) was also slurried in a separate 10 mL Et20. The lithium salt was then added slowly into the ZrCl4slurry. The reaction was then stirred overnight. In the morning, the solvent was removed. The residual solid was stirred in 20 mL pentane for 1 hour, filtered, and dried. The collected solid was then stirred in 20 mL dichloromethane for 1 hour and filtered to remove LiCl. The dichloromethane was then removed to give pure product. Yield was determined to be 0.177 g (71%).

[0191] The1H NMR of Structure 36 was determined to be (400 MHz, Methylene Chloride-d2) 5 7.79 (s, 8H), 7.67 - 7.53 (m. 2H), 7.36 (dd. J = 6.9, 0.8 Hz, 2H). 7.13 - 6.94 (m, 4H), 2.32 (s, 6H), 2.09 (s, 6H), 1.99 (s, 6H), 1.93 (s, 6H), 1.89 (s, 6H), 1.24 (s, 6H), 1.13 (s, 6H).Example 2

[0192] In this example, the 11-14 organometallic metallocene catalysts comprising at least one binuclear indacene group prepared in Example 1 were tested for polymerization activity for polypropylene and ethylene-propylene co-polymer.

[0193] Polymerization procedure: Propylene polymerizations were carried out under high-throughput conditions according to the following general procedure. A pre-weighed glass vial insert, and disposable stirring paddle were fitted to each reaction vessel of the reactor, which contains 48 individual reaction vessels. The reactor was then closed, and ethylene gas wasintroduced at a desired pressure. Then solvent (typically the isohexane) was added to bring the total reaction volume, including the subsequent additions, to 5 mL and the reactor vessels were heated to their set temperature (usually from about 50°C to about 110°C). The contents of the vessel were stirred at 800 rpm. An activator solution (typically 100-1000 molar equivalents of methyl alumoxane (MAO) in toluene) was then injected into the reaction vessel along with 500 microliters of toluene, followed by addition of 1 -octene (typically 20-160 pL). Catalyst (typically 0.50 mM in toluene, such as 20-40 nmol of catalyst) and another aliquot of toluene (500 microliters) were then added to initiate the reaction. Equivalence is determined based on the mol equivalents relative to the moles of the transition metal in the catalyst complex. The reaction was then allowed to proceed until a pre-determined amount of pressure had been taken up by the reaction. Alternatively, the reaction may be allowed to proceed for a set amount of time. At this point, the reaction was quenched by pressurizing the vessel with compressed air. After the polymerization reaction, the glass vial insert containing the polymer product and solvent was removed from the pressure cell and the inert atmosphere glove box, and the volatile components were removed using a Genevac HT-12 centrifuge and Genevac VC3000D vacuum evaporator operating at elevated temperature and reduced pressure. The vial was then weighed to determine the yield of the polymer product. The resultant polymer was analyzed by Rapid GPC (see below) to determine the molecular weight and by DSC (see below) to determine melting point.

[0194] Autoclave polymerization: Supported catalyst (ca. 0.5-0.6 g) was slurried into dry and degassed mineral oil to yield a slurry that contains 5% by weight of supported catalyst. The supported catalysts were added to the reactor as a slurry in oil. The catalyst slurry containing certain amounts of catalysts was injected using 400 mL propylene into a 2 L autoclave reactor containing propylene (400 mL) (total propylene 800 mL), I L (2 or 8 mmol) and triisobutylaluminum (TIBAL, 1.0 ml of a IM solution), at ambient temperature for 5 minutes. Subsequently, the reactor temperature was raised to about 70°C and the polymerization was run for an allotted period of time typically about 30 minutes. After the allotted time the reactor was cooled to room temperature and vented.

[0195] Rapid GPC procedure: To determine various molecular weight related values by gel permeation chromatography (GPC), high temperature size exclusion chromatography was performed using an automated Rapid GPC. This apparatus has a series of three 30 cm x 7.5 mm linear columns, each containing PLgel 10 pm, Mix B. The GPC system was calibrated using polystyrene standards ranging from 580 - 3,390,000g / mol. The system was operated at an eluent flow rate of 2.0 mL / minutes and an oven temperature of 165°C. 1,2, 4-tri chlorobenzenewas used as the eluent. The polymer samples were dissolved in 1, 2, 4-tri chlorobenzene at a concentration of 0.1 - 0.9 mg / mL. 250 uL of a polymer solution was injected into the system. The concentration of the polymer in the eluent was monitored using an evaporative light scattering detector (as shown by the examples in Table 3) or Polymer Char IR4 detector. The molecular weights presented are relative to linear polystyrene standards and are uncorrected.

[0196] DSC Procedure: For the high throughput samples, the melting temperature (Tm) w as measured using Differential Scanning Calorimetry (DSC) using commercially available equipment such as a TA Instruments TA-Q200 DSC. Typically, 5 to 10 mg of molded polymer or plasticized polymer is sealed in an aluminum pan and loaded into the instrument at about room temperature. Samples w ere pre-annealed at about 220°C for about 15 minutes and then allowed to cool to about room temperature overnight. The samples were then heated to about 220°C at a heating rate of about 100°C / min. held at this temperature for at least about 5 minutes, and then cooled at a rate of about 50°C / min to a temperature typically at least about 50°C below the crystallization temperature. Melting points were collected during the heating period.

[0197] 'H NMR procedure: 'H NMR data of catalysts and ligands w ere collected at 23°C using a 5 mm tube on a 400 MHz Bruker spectrometer with deuterated methylene chloride (CD2CI2), benzene (CeDe) or THF (thf-dS). Data was recorder with a 30° pulse with either 8 or 16 transients.

[0198] 'H NMR data of the polymer can be collected at 120°C using a 10 mm cry oprobe on a 600 MHz Bruker spectrometer with deuterated tetrachloroethane (tce-d2). Samples were prepped with a concentration of 30 mg / mL at 140°C. Data was recorded with a 30° pulse, 5 second delay, 512 transients. Signals were integrated and the numbers of unsaturation types per 1000 carbons were reported. The shift regions for unsaturations were determined from Table 1.Table 1Number ofRegionhydrogens Unsaturation Type (PPm) per structureVinyl 4.95-5.10 2Vinylidene 4.70-4.84 2Vinylene 5.31-5.55 2Trisubstituted 5.11-5.30 1

[0199] Peak melting point, Tm, described for reactor batches (also referred to as melting point) and peak crystallization temperature, Tc, (also referred to as crystallization temperature) are determined using the following DSC procedure according to ASTM D3418-03. Differential scanning calorimetric (DSC-2) data can be obtained using a TA Instruments model DSC2500 machine. Samples weighing approximately 5 mg 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 about 200°C at a rate of about 10°C / minute. The sample is kept at about 200°C for 5 minutes, then cooled to about -50°C at a rate of about 10°C / minute, followed by an isothermal for about 5 minutes and heating to about 200°C at about 10°C / minute, holding at about 200°C for about 5 minutes and then cooling down to about 25°C at a rate of about 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. In the event of conflict between the DSC Procedure-1 and DSC procedure-2, DSC procedure-2 is used.

[0200] 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 multiplechannel band filter based infrared detector ensemble IR5 with band region covering from about 2700 cm’1to about 3000 cm’1(representing saturated C-H stretching vibration), an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-pm Mixed-B LS columns are used to provide polymer separation. Reagent grade 1,2,4-tri chlorobenzene (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 pL. 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=al, where a is the mass constant determined w-ith polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography overelution 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 using Equation 1.Equation 1 log M = (aPS+ 1) / (a + 1) × log MPS- log(KPS / K) / (a + 1)log M = (aPS+ 1) / (a + 1) × log MPS- log(KPS / K) / (a + 1)a + 1 a + 1

[0201] where the variables with subscript “PS"’ stand for polystyrene while those without a subscript are for the test samples. In this method, aps = 0.67 and Kps = 0.000175, a and K for other materials are as calculated and published in literature (Sun. T. et al. Macromolecules 2001, 34, 6812), except that for purposes of this present disclosure and claims thereto, a = 0.705 and K = 0.0000229 for ethylene-propylene copolymers and ethylene-propylene- diene terpolymers, a = 0.695 and K = 0.000579 for linear ethylene polymers, a = 0.705 and K = 0.0002288 for linear propylene polymers, and a = 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.

[0202] The results of the polymerization and subsequent testing are shown in Table 2 and FIG. 4-6. Table 2 includes ethylene-propylene polymerization (EP) and propylene polymerization (PP) data for comparative catalysts Ci-Cs and the organometallic metallocene catalysts comprising at least one binuclear indacene group 11-14. FIG. 4 is a bar graph comparing mean molecular weight in g / mol for each class of catalyst tested. FIG. 5 is a bar graph comparing mean activity in kg / mmol / h for each class of catalyst tested. FIG. 6 is a bar graph comparing mean melting temperature Tm for each class of catalyst tested.Table 2Catalyst Activity Mn MwClass Polymer PDI Tm (°C) ID (kg / mmol / h) (g / mol) (g / mol)Ci binuclear-indene EP 265.9 70,370 135,033 1.9Ci binuclear-indene EP 271.7 65,684 135,717 2.1Cl binuclear-indene EP 275.6 69,733 136,950 2.0Cl binuclear-indene PP 54.4 59,565 131,650 2.2 150.0 Cl binuclear-indene PP 55.9 55,089 119,964 2.2 150.0 Cl binuclear-indene PP 56.2 59,927 139,460 2.3 150.0 C2binuclear-indene EP 412.9 48,946 104,330 2.1C2binuclear-indene EP 420.9 57,196 122,662 2.1C2binuclear-indene EP 446.8 58,395 103,681 1.8c2binuclear-indene PP 57.6 46,183 121,794 2.6 149.0 C2binuclear-indene PP 59.6 59,078 125,404 2.1 149.0 c2binuclear-indene PP 57.8 54,871 115,723 2.1 149.5 c3binuclear-indene PP 20.6 44,747 91,550 2.0 150.1 c3binuclear-indene PP 14.8 53,422 95,028 1.8 151.1 C3binuclear-indene PP 30.0 47,528 92,721 2.0 149.7 c4mono-nuclear PP 77.0 67,883 106,374 1.6 148.7 c4mono-nuclear PP 120.2 56,609 99,221 1.8 148.6 c4mono-nuclear PP 168.9 45,700 82,404 1.8 147.2 c4mono-nuclear EP 873.4 61,828 113,955 1.8 c4mono-nuclear EP 870.5 61,818 114,496 1.9 c4mono-nuclear EP 930.8 69,174 124,738 1.8 c5mono-nuclear PP 294.1 44,084 85.430 1.9 152.0 c5mono-nuclear PP 354.0 44,885 93,480 2.1 151.7 c5mono-nuclear PP 332.9 44,116 82.375 1.9 151.4 c5mono-nuclear EP 454.9 75,019 155,326 2.1 c5mono-nuclear EP 572.1 64,960 128,151 2.0 c5mono-nuclear EP 347.4 90,099 159,313 1.8 C6mono-nuclear PP 299.3 52,683 94,844 1.8 156.3 c6mono-nuclear PP 273.9 40,924 90,750 2.2 154.6 c6mono-nuclear PP 342.1 38,319 90,712 2.4 154.8 c6mono-nuclear EP 28.6 61,174 150,197 2.5 c6mono-nuclear EP 46.5 58,127 159,035 2.7 c6mono-nuclear EP 38.3 69,798 147,640 2.1 c7mono-nuclear PP 298.8 52,281 88,421 1.7 156.2 c7mono-nuclear PP 293.2 48,462 83.617 1.7 155.2 c7mono-nuclear PP 298.4 46,553 81,587 1.8 154.8 c7mono-nuclear EP 515.3 43,360 109,459 2.5 c7mono-nuclear EP 224.6 44,307 98,421 2.2 c7mono-nuclear EP 942.0 47,561 110,371 2.3 c8mono-nuclear PP 241.2 22,474 37,687 1.7 139.3 C8mono-nuclear PP 255.3 20,305 37,382 1.8 139.6 C8mono-nuclear PP 244.3 19,613 35,708 1.8 139.6 c8mono-nuclear EP 1387.1 36,468 94,412 2.6 c8mono-nuclear EP 1395.8 29,301 87,196 3.0 c8mono-nuclear EP 1326.9 38,252 91,409 2.4II binuclear- EP 276.7 88,642 188,209 2.1 indaceneII binuclear- EP 257.5 123,279 229,881 1.9 indaceneII binuclear- EP 284.7 104,752 203,835 1.9 indaceneII binuclear- PP 62.1 63,512 129,446 2.0 153.9 indaceneII binuclear- PP 62.9 57,893 130,648 2.3 154.4 indaceneII binuclear- PP 61.5 61,924 122,541 2.0 154.7indacenebinuclear- 12 EP 613.9 53,518 103,455 1.9indacenebinuclear- 12 EP 647.6 42,801 100,717 2.4indacenebinuclear- 12 EP 613.5 46,047 97,915 2.1indacenebinuclear- 12 PP 124.4 44,863 97,271 2.2 152.8 indacenebinuclear- 12 PP 121.9 51,765 102,107 2.0 152.3 indacenebinuclear- 12 PP 70.6 47,817 103,700 2.2 152.3 indacenebinuclear- 13 EP 184.6 112,713 198,895 1.8indacenebinuclear- 13 EP 190.3 101,380 195,109 1.9indacenebinuclear- 13 EP 174.8 98,609 197,423 2.0indacenebinuclear- 13 PP 51.8 66,705 138,410 2.1 154.3 indacenebinuclear- 13 PP 49.1 63,861 138,115 2.2 154.7 indacenebinuclear- 13 PP 49.5 71,777 145,059 2.0 154.4 indacenebinuclear- 14 EP 689.2 53,270 108,995 2.0indacenebinuclear- 14 EP 671.4 48,855 119,907 2.5indacenebinuclear- 14 EP 604.4 55,383 109,798 2.0indacenebinuclear- 14 PP 102.9 60,019 153,416 2.6 153.6 indacenebinuclear- 14 PP 105.8 51,674 120,191 2.3 153.9 indacenebinuclear- 14 PP 129.5 58,841 134,305 2.3 153.4 indaceneTable 3C H2Catalystatalyst Mn Mw MzCatalyst activity MWD Tm Tc (mmol) (g / mol) (g / mol) (g / mol) (°C) (°C) (mg) (g / g / h)25.5 8 5.240 32,490 112,644 262,874 3.47 149.3 114.4 Ci25.3 2 2.836 50,347 181,584 411,694 3.61 149.7 105.7 Ci25.0 8 4,752 32,814 113,614 241,581 3.46 151.0 106.9 c225.8 2 2,072 50,375 186,317 416,327 3.70 150.8 105.8 c2Il 25.7 8 5.121 32,712 118,231 280,015 3.61 154.3 108.7 II 25.7 2 3.041 47,344 185,756 455,519 3.92 155.5 108.6 12 25.0 8 7,295 37,243 150,624 343,379 4.04 155.5 109.5 12 25.3 2 4,126 52,668 237,232 531,989 4.50 156.4 109.0Table 40 / 0 / 0 / 0 / / o / o / o / oCatalyst mmmm 1,2- 2,1- vinylene trisubstituted vinyls vinyledene stereoerrors re gioerrors 7.1% 26.2% 38.1% 28.6% 0.886 245 15 Sup -Ci2.8% 22.2% 41.7% 33.3% 0.898 215 16 Sup-Ci8.5% 30.5% 35.6% 25.4% 0.877 265 14 Sup-C25.7% 24.5% 35.8% 34.0% 0.898 217 13 Sup-C27.4% 24.1% 40.7% 27.8% 0.919 172 9 Sup-118.9% 26.8% 37.5% 26.8% 0.920 166 11 Sup-11Sup-12 6.7% 24.4% 37.8% 31.1% 0.932 139 10 Sup-12 4.0% 26.0% 40.0% 30.0% 0.927 154 10

[0203] As shown in Table 2 and summarized in FIG. 4-6, the disclosed binuclear indacene catalysts provide improvements to ethylene-propylene copolymer molecular weight. For example, binuclear indacene catalyst II (phenyl linked) provided significant improvement to molecular weight as compared to its indene analog Ci and both indenyl or indacenyl mononuclear analogs. This unprecedented effect is not observed with 4,4-biphenyl analogs C2 and 12, thus indicating direct tie of this effect to phenyl linker in the 4 position. In addition, it was observed that indacene mononuclear systems provide improved PP melting points over mononuclear indenyl analogs. However, this effect is further improved in binuclear indacenyl systems where catalysts 11-14 provided on average about 4°C difference in polymer melting point relative to both mononuclear and binuclear comparatives.

[0204] Table 3 shows data for representative supported catalysts. The data indicates that catalysts II and 12 provide generally improved activity and melting points of polypropylenes over C1and C2.

[0205] Table 4 is 13c and 1H NMR analysis of polymers prepared with supported catalysts Ci, C2, Il and 12. The data shows improved isotacticity (mmmm) and higher stereo and regioselectivity for catalysts II and 12.

[0206] While the 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 disclosure as disclosed herein. Although individual embodiments are discussed, the present disclosure covers all combinations of all those embodiments.

[0207] While compositions, methods, and processes are described herein in terms of “comprising,” “containing,” “having,” or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. 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 disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[0208] All numerical values within the detailed description are modified by “about” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary' skill in the art.

[0209] Many alterations, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description without departing from the spirit or scope of the present disclosure and that when numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated.

Claims

CLAIMS:

1. A catalyst compound represented by the formula:wherein:M is a transition metal atom selected from group 3, 4, or 5 of the Periodic Table of Elements,L is a linking group selected from the group consisting of single covalent bond, C1-C20 hydrocarbylene group, and divalent ferrocene,each X is a univalent anionic ligand, or two adjacent X's comprise a C2-C20 hydrocarbylene group bound to transition metal atom M to form a metallocycle ring, or two adjacent X’s form a chelating ligand, or two adjacent X’s form a C2-C20 diene ligand;R1, R2, and R3are each independently selected from a hydrogen atom, an unsubstituted Ci to C20 hydrocarbyl group, or a substituted Ci to C20 hydrocarbyl group,R4, R5, R6and R7are each independently selected from a hydrogen atom, an unsubstituted Ci to C20 hydrocarbyl group, or a substituted or unsubstituted Ci to C20 hydrocarbyl group, andJi and J2 are fused to form a C1-C20 cyclic ring.

2. The catalyst compound of claim 1, wherein M is zirconium.

3. The catalyst compound of any of claims 1-2, wherein each X is chloride.

4. The catalyst compound of any of claims 1-3, wherein L is the C1-C20 hydrocarbylene group and wherein L further comprises a linker group selected from the group consisting of divalent aryl group, C1-C20 substituted divalent aryl group, divalent fluorenyl group, C1-C20 substituted divalent fluorenyl group, divalent naphthalene group, and C1-C20 substituted divalent naphthalene group.

5. The catalyst compound of any of claims 1-3, wherein L is the C1-C20 hydrocarbylene group and wherein L further comprises a linker group selected from the group consisting of divalent bi-phenyl group and C1-C20 substituted divalent bi-phenyl group.

6. The catalyst compound of any of claims 1-5, wherein the catalyst compound is unbridged and T is not present.

7. The catalyst compound of any of claims 1-5 wherein:T is represented by the formula (R*2G)g,each G is C, Si, or Ge,g is 1 or 2, andeach R* is, independently selected from hydrogen, halogen, Ci to C20 hydrocarbyl, or Ci to C20 substituted hydrocarbyl.

8. The catalyst compound of claim 7, wherein two or more R* form an aromatic or a partially saturated or saturated cyclic or fused ring system.

9. The catalyst compound of any of claims 1-8, wherein R4and R5are joined to form a cyclic structure.

10. The catalyst compound of any of claims 1-9 wherein Ji and J2 are fused to form a compound selected from the group consisting of 1,5,6, 7-tetrahydro-s-indacenide, 6,6-dimethyl- 1.5.6.7-tetrahydro-s-indacen-l-ide, 5,5,7,7-tetramethyl-l,5,6,7-tetrahydro-s-indacen-l-ide, 5.6.7.8-tetrahydro-lH-cyclopenta[b]naphthalen-l-ide, 5,6,7,8-tetrahydro-lH-5,8- methanocyclopenta[b]naphthalen-l-ide, 5.6,7,8-tetrahydro-lH-5,8- ethanocyclopenta[b]naphthalen-l-ide, 5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-lH- cyclopenta[b]naphthalen-l-ide, l,5,6,7,8,9-hexahydrocyclohepta[f|inden-l-ide, and combinations thereof.

11. The catalyst compound of claim 1 wherein the catalyst compound is represented by any one of the following structures:

12. A catalyst system comprising an activator and a catalyst compound represented by the formula:wherein:M is a transition metal atom selected from group 3, 4, or 5 of the Periodic Table of Elements,L is a linking group selected from the group consisting of single covalent bond, C1-C20 hydrocarbylene group, and divalent ferrocene,each X is a univalent anionic ligand, or two adjacent X’s comprise a C2-C20 hydrocarbylene group bound to transition metal atom M to form a metallocycle ring, or two adjacent X’s form a chelating ligand, or two adjacent X’s form a C2-C20 diene ligand;R1, R2, and R3are each independently selected from a hydrogen atom, an unsubstituted Ci to C20 hydrocarbyl group, or a substituted Ci to C20 hydrocarbyl group,R4, R3, R6and R7are each independently selected from a hydrogen atom, an unsubstituted Ci to C20 hydrocarbyl group, or a substituted or unsubstituted Ci to C20 hydrocarbyl group, andJi and J2 are fused to form a C1-C20 cyclic ring.

13. The catalyst system of claim 12, wherein the catalyst compound is unbridged and T is not present or wherein:T is represented by the formula (R*2G)g,each G is C, Si, or Ge,g is 1 or 2, andeach R* is, independently selected from hydrogen, halogen. Ci to C20 hydrocarbyl, or Ci to C20 substituted hydrocarbyl, and optionally, wherein two or more R* form an aromatic or a partially saturated or saturated cyclic or fused ring system.

14. The catalyst system of any of claims 12-13, wherein R4and R' are joined to form a cyclic structure.

15. The catalyst system of any of claims 12-14, wherein the activator comprises at least one of aluminoxane or salts of non-coordinating anions.

16. The catalyst system of claim 15, wherein the salts of non-coordinating anions is represented by the formula: (Z)d+ (Ad-) wherein Z is (L-H) or a reducible Lewis Acid, L is a Lewis base; H is hydrogen; (L-H)+ is a Bronsted acid; Ad- is a non-coordinating anion having charge d-; and d is an integer from 1 to 3.

17. The catalyst system of claim 15, wherein salts of non-coordinating anions is represented by the formula:(Z)d+ (Ad-)whereinAd- is a non-coordinating anion having a charge d-;d is an integer from 1 to 3, andZ is a reducible Lewis acid represented by the formula: (Ar3C+), and wherein Ar is aryl or aryl substituted with a heteroatom, a Ci to C40 hydrocarbyl, or a substituted Ci to C40 hydrocarbyl.

18. The catalyst system of claim 13, wherein the activator comprises aluminoxane and the aluminoxane is present in a ratio of about 1: 100 to about 1: 2000 relative to M.

19. The catalyst system of any of claims 12-18, further comprising a support material selected from the group consisting of AI2O3, ZrQ?. SiCL, SiCh / AhCh, SiCh / TiCh, silica clay, silicon oxide / clay, and combinations thereof.

20. The catalyst system of claim 12 wherein the catalyst compound is represented by any¬ one of the following structures:

21. A method comprising:introducing one or more of a C2 to C20 olefin monomer, and a catalyst system of any one of claims 12-20, and optionally hydrogen into a reactor at a reactor pressure of from 0.7 bar to 70 bar and a reactor temperature of from 20°C to 150°C; andpolymerizing the C2 to C20 olefin monomer to obtain a polymer or copolymer.

22. The method of claim 21 wherein the C2 to C20 olefin monomer comprises at least one monomer selected from the group consisting of ethylene, propylene 1 -butene, 1 -pentene, 1 -hexene, 2-methyl-l -pentene. vinylcyclobutane. 1 -heptene, 1 -octene, 1 -decene, 1,5 -hexadiene, 1.7-octadiene and 1,9-decadiene, norbomene, vinylnorbomene, ethylidine norbomene, and combinations thereof23. The method of any of claims 20-21. wherein the polymer or copolymer has a Mw value of 1,000 to 1,000,000 g / mol as measured by gel permeation chromatography.

24. The method of any of claims 20-22, wherein the polymer or copolymer has a Mw distribution with poly dispersity index less than 10.

25. The method of any of claims 20 to 24, wherein the polymer or copolymer has a melting point at a point in a range of about 120°C to about 200°C.

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