Julolidine substituted metallocene catalysts

Abstract

Disclosed herein are metallocene catalyst compounds and catalyst systems comprising at least one julolidine substitution. Further disclosed herein are methods of using the julolidine substituted metallocene catalyst compounds in slurry-phase polymerization.

Description

JULOLIDINE SUBSTITUTED METALLOCENE CATALYSTS CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to us provisional application no.63 / 717134 filed November 6, 2024, the disclosure of which is incorporated herein by reference.FIELD

[0002] The subject matter disclosed herein relates to metallocene catalyst compounds and catalyst systems comprising at least one julolidine substitution, as well as uses thereof in olefin polymerization applications.BACKGROUND

[0003] 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

[0004] 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; T is a bridging group; each of X1and X2is a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring; R1, R2, R3, and R4are each independently selected from a hydrogen atom, substituted Ci to Ce hydrocarbyl group, or unsubstituted Ci to Ce hydrocarbyl group and, optionally, wherein any adjacent R1, R2, R3and R4are joined to form a cyclic structure; R5- R21are each independently selected from a hydrogen atom, a substituted Ci to Ce hydrocarbyl group, or unsubstituted Ci to C20 hydrocarbyl group; Y is nitrogen or phosphorus; and J1and J2are each are each independently selected from a hydrogen atom, substituted Ci to Ce hydrocarbyl group, or unsubstituted Ci to C20 hydrocarbyl group and, optionally, Ji and J2 are fused to form cyclic or polycyclic structure.

[0005] Further disclosed herein catalyst system comprising a catalyst compound represented by any of the following formulas:

[0006] Further disclosed herein is an example 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 an alpha olefin polymer or copolymer.

[0007] 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

[0008] 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:

[0009] 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.

[0010] FIG. 2 is a set of chemical structures representing comparative catalysts Ci, C2, C3, C4, Cs, Ce, C7, Cs, and C9, in accordance with certain embodiments of the present disclosure.

[0011] FIG. 3 is a general synthetic synthesis scheme for julolidine-based catalysts, in accordance with certain embodiments of the present disclosure.

[0012] FIG. 4 is a general synthetic synthesis scheme for julolidine-based catalysts, in accordance with certain embodiments of the present disclosure.

[0013] 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.

[0014] 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

[0015] Disclosed herein are metallocene catalyst compounds and catalyst systems comprising at least one julolidine substitution. Further disclosed herein are methods of using the julolidine substituted metallocene catalyst compounds in gas-phase polymerization.

[0016] 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.

[0017] 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.

[0018] 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 C3 to C20 a-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.

[0019] 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 torefer 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.

[0020] 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.

[0021] 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 activators of the present disclosure are intended to embrace ionic forms in addition to the neutral forms of the compounds / components.

[0022] A metallocene catalyst is an organometallic compound with at least one n-bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) and more frequently two K-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

[0023] Embodiments of the catalysts disclosed herein are organometallic metallocene complexes having at least one julolidine-based ligand. The catalyst embodiments disclosed herein unexpectedly demonstrate excellent activity and improved hydrogen response. In addition to this, the catalysts disclosed herein show improved molecular weight capability of propylene homopolymers and copolymers.

[0024] Embodiments of the julolidine-based catalysts described herein are generally represented by Structure 1:Structure 1 wherein M is a transition metal atom selected from group 3, 4, or 5 of the Periodic Table of Elements, T is a bridging group, each of X1and X2is a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring, R1, R2, R3, and R4are each independently a hydrogen atom or substituted or unsubstituted Ci to Ce hydrocarbyl group and, optionally, any adjacent R1, R2, R3and R4can be joined to form a cyclic structure, R5- R21are each independently a hydrogen atom or a substituted or unsubstituted Ci to C20 hydrocarbyl group, Y is nitrogen or phosphorus, Ji and J2 are each are each independently a hydrogen atom or substituted or unsubstituted Ci to C20 hydrocarbyl group and, optionally, Ji and J2 are fused to form cyclic or polycyclic structure.

[0025] Further embodiments of julolidine based catalysts are generally represented by Structure 2:Structure 2 wherein M is a transition metal atom selected from group 3, 4, or 5 of the Periodic Table of Elements, T is a bridging group, each of X1and X2is a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring, R3, and R4are each independently a hydrogen atom or substituted or unsubstituted Ci to Ce hydrocarbyl group and, R5- R21and R23are each independently a hydrogen atom or a substituted or unsubstituted Ci to C20 hydrocarbyl group, J1and J2are each are each independently a hydrogen atom or substituted or unsubstituted Ci to C20 hydrocarbyl group and, optionally, J1and J2are fused to form cyclic or polycyclic structure. R22may be substituted or unsubstituted C1-C30 hydrocarbyl group such as alkyl, phenyl or substituted or unsubstituted julolidyl group.

[0026] In embodiments, T may be 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 hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a Ci to C20 substituted hydrocarbyl, and two or more R* can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.

[0027] In embodiments T is a bridging group and is represented by R'2C, R'2Si, R'2Ge, R'2CCR'2, R'2CCR'2CR'2, R'2CCR'2CR'2CR'2, R'C=CR', R'C=CR'CR'2, R'2CCR'=CR'CR'2, R'C=CR'CR— CR', R'C=CR'CR'2CR'2, R'2CSiR'2, R2CSiR'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— CR2CR'2, R'2C— Se— CR'=CR', R'2C— N=CR', R'2C— NR'— CR'2, R'2C— NR'— CR'2CR'2, R'2C— NR'— CR — CR', R'2CR'2C— NR'— CR'2CR'2, R'2C— P=CR', or R'2C — PR' — CR'2, where each R' is, independently, hydrogen or a Ci to C2o containing hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), 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 is a bridging group comprising carbon or silica, such as dialkylsilyl. In some embodiments T may be selected from CH2, CH2CH2, C(CH3)2, SiMe2, SiPh2SiMePh, silylcyclobutyl (Si(CH2)3), (Ph)2C, (p-(Et)3SiPh)2C, and cyclopentasilylene (Si(CH2)4) (Si(CH2)4).

[0028] In embodiments of any formula described herein, T may be represented by the formula Ra2J, where J is C, Si, or Ge, and each Ra is, independently, hydrogen, halogen, Ci to C2o hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a Ci to C2o substituted hydrocarbyl, and two Ra can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system. In another aspect, in any embodiment of any formula described herein T may be CH2, CH2CH2, C(CH3)2, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, or Si(CH2)5.

[0029] A non-limiting set of example julolidine-based catalysts (11-18) is illustrated in FIG. 1 which were synthesized and compared against a number of comparative metallocene catalysts (Ci-Ce) illustrated in FIG. 2.Representative Synthesis

[0030] FIG. 3 is a general synthetic synthesis scheme for embodiments of the 11-16 julolidine-based catalysts illustrated in FIG. 1. FIG. 4 is a general synthetic synthesis scheme for embodiments of the 17 and 18 julolidine-based catalysts illustrated in FIG. 1.

[0031] In FIG. 3 and FIG. 4, optionally the structure includes a fused ring in the 5,6 position of indene parent fragment. For each scheme, the first step comprises borylation of julolidine and / or a hetero-atom substituted julolidine analog using a borylation agent comprising bis(pinacolato)diboron and (l,5-cyclooctadiene)(methoxy)iridium(I) dimer. In embodiments, the julolidine and / or hetero-atom substituted julolidine analog include substitutions at one or more carbon positions. The borylation step results in a BPin analog of the julolidine and / or hetero-atom substituted julolidine analog.

[0032] The second step comprises reacting the BPin analog with a Br-substituted indene in a Suzuki cross-coupling reaction to afford a 4-julolidyl substituted indenyl fragments. In embodiments, the Br-substituted indene includes one or more substitutions at one or more carbon positions.

[0033] The third step comprises lithiating the 4-julolidyl substituted indenyl fragments with nBuLi to afford a lithiated 4-julolidyl substituted indenyl fragments.

[0034] In Fig. 3, the fourth step comprises reacting the lithiated 4-julolidyl substituted indenyl fragments with substituted cyclopentadienyl fragments containing a bridging group T and a leaving group (LG) to yield neutral ligands. In some embodiments, the Me4CpSiMe2OTf includes dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl trifluoromethanesulfonate.

[0035] In Fig. 4, the fourth step comprises reacting the lithiated 4-julolidyl substituted indenyl fragments with substituted aryl indenyl or julolidyl indenyl fragment containing a bridging group T and a leaving group LG to yield neutral ligands. In some embodiments, the fourth step comprises reacting the lithiated 4-julolidyl substituted indenyl fragments with [dimethyl-(2-methyl-4-phenyl-l,5,6,7-tetrahydro-s-indacen-l-yl)silyl] tritiate and [dimethyl-(2-methyl-4-tetramethyljulolidyl-l,5,6,7-tetrahydro-s-indacen-l-yl)silyl] chloride.

[0036] In both Fig. 3 and Fig. 4, the fifth step includes lithiating the neutral ligand product from the fourth step with nBuLi.

[0037] In the sixth step, the product from the fifth step is metallated with Group (IV) metal salt such as NOG where M is the Group (IV) metal to afford final complexes 11-18. In some embodiments the sixth step involves reacting product from fifth step with zirconium tetrachloride. With complexes 17 and 18, diastereomer formation (rac and meso) is expected. Such isomers may be separated with fractional crystallization.Activators

[0038] The terms “cocatalyst” and “activator” are used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation. 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, c-bound, metal ligand making the metal complex cationic and providing a charge-balancing non-coordinating or weakly coordinating anion.

[0039] In one embodiment, alumoxane activators are utilized as an activator in the catalyst composition. Alumoxanes are generally oligomeric compounds containing — A1(RX) — O — subunits, where R1is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. 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 3 A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3 A).

[0040] 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 greater than 1: 100 relative to the Group 4 metal of the catalyst (e.g., greater than 1:250, or greater than 1:500).

[0041] 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.

[0042] 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.

[0043] 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: (AnC+), wherein Ar is aryl or aryl substituted with a heteroatom, a Ci to C40 hydrocarbyl, or a substituted Ci to C40 hydrocarbyl.

[0044] 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)b orate, 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.

[0045] 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

[0046] In embodiments herein, the catalyst system may comprise an inert support material. 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.

[0047] 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 (SiO?), alumina (AI2O3), and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with silica or aluminainclude magnesia, titania (TiCh), zirconia (ZrCh), 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, silica-chromium, silica-alumina, silica-titania, and the like. In some embodiments, support materials include AI2O3, ZrCh, SiC>2, and combinations thereof, while in other embodiments, the support material includes SiC>2, AI2O3, or SiCh / AhCh.

[0048] 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 that ranges from 5 to 500 micrometers (pm). 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 pm. 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 pm. 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.

[0049] 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.

[0050] The calcined support material is subsequently contacted with at least one polymerization catalyst comprising at least one metallocene compound 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 a metallocene compound and an activator. In some embodiments, the slurry of the support material is first contacted with the activator and a trialkylaluminum promoter for a period of time ranging from0.1 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 metallocene compound 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.

[0051] In certain embodiments, the mixture of the metallocene, activator, and support is heated in the temperature 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).

[0052] 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

[0053] 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 metallocene compound, as described above. The catalyst compound and activator may be combined in any order and are typically combined prior to contacting the monomer.

[0054] 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 Ce 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.

[0055] 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, norbornene, norbomadiene, di cyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, 2-methyl-l -pentene, vinylcyclobutane, 1,5 -hexadiene, 1,7-octadiene, 1,9-decadiene, substituted derivatives thereof, and isomers thereof. In certain embodiments, a non-limiting list of examples C2 to C40 olefin monomers and optional comonomers includes: hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, l-hydroxy-4-cyclooctene, l-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbomene, norbomadiene, and their respective homologs and derivatives. In certain embodiments, a non-limiting list of examples C2 to C40 olefin monomers and optional comonomers includes norbomene, norbomadiene, and dicyclopentadiene.

[0056] 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).

[0057] 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 alkyl substituted aromatic compounds (e.g., benzene, toluene, mesitylene, and xylene). Suitable solvents also includeliquid olefins that may act as monomers or comonomers, including ethylene, propylene, 1 -butene, 1 -hexene, 1 -pentene, 3 -methyl- 1 -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, less than 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).

[0058] 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 to 250 minutes, or from 10 to 120 minutes).Polyolefin Products

[0059] This disclosure also relates to compositions of matter produced by the methods described herein.

[0060] 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 to 50 mol% (e.g., from 0.5 to 50 mol%, from 1 to 30 mol%, from 5 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 to 50 mol% (e.g., from 0.5 to 50 mol%, from 1 to 30 mol%, from 5 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 producedmay be isotactic polypropylene, atactic polypropylene having random, block, or impact copolymers.

[0061] 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, or less than 3. In some embodiments, these homopolymers or copolymers have a melting point (Tm) less than 135°C. In some embodiments, a copolymer product has a comonomer content 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

[0062] 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.

[0063] 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.

[0064] The polymers produced herein may be further blended with one or more second polymers and used in film, molded part and other typical 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 additionto 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-type catalysts, chromium catalysts, metallocene-type catalysts, other appropriate catalyst systems or combinations thereof, or by free-radical polymerization.Additional Embodiments

[0065] 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.

[0066] 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; T is a bridging group; each of X1and X2is a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring; R1, R2, R3, and R4are each independently selected from a hydrogen atom, substituted Ci to Ce hydrocarbyl group, or unsubstituted Ci to Ce hydrocarbyl group and, optionally, wherein any adjacent R1, R2, R3and R4are joined to form a cyclic structure; R5- R21are each independently selected from a hydrogen atom, a substituted Ci to Ce hydrocarbyl group, or unsubstituted Ci to C20 hydrocarbyl group; Y is nitrogen or phosphorus; and J1and J2are each are each independently selected from a hydrogen atom, substituted Ci toCe hydrocarbyl group, or unsubstituted Ci to C20 hydrocarbyl group and, optionally, J1and J2are fused to form cyclic or polycyclic structure.

[0067] Embodiment 2. The catalyst compound of embodiment 1 represented by the formula:wherein R22is a substituted or unsubstituted C1-C30 hydrocarbyl or substituted or unsubstituted julolidyl group, R23is a hydrogen atom or a substituted or unsubstituted Ci to C20 hydrocarbyl group, and J1and J2are each are each independently selected from a hydrogen atom or substituted or unsubstituted Ci to C20 hydrocarbyl group and, optionally, J1and J2are fused to form cyclic or polycyclic structure.

[0068] Embodiment 3. The catalyst compound of embodiment 1 or 2, wherein R5is a primary substituted or unsubstituted C1-C12 alkyl group.

[0069] Embodiment 4. The catalyst compound of any of embodiments 1-3, wherein R6and R7are a hydrogen atom.

[0070] Embodiment 5. The catalyst compound of any of embodiments 1-4, 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 selected from hydrogen, halogen, Ci to C20 hydrocarbyl, or a Ci to C20 substituted hydrocarbyl, and optionally wherein two or more R* form a cyclic structure individually selected from aromatic, partially saturated, saturated cyclic, or fused ring system.

[0071] Embodiment 6. The catalyst compound of any of embodiments 1-5, wherein Y is nitrogen and R7- R21are independently selected from hydrogen or a primary substituted or unsubstituted C1-C12 alkyl group.

[0072] Embodiment 7. The catalyst compound of embodiment 6, wherein Y is nitrogen and R6, R7, R8, R9, R14-R21are hydrogen and R10- R13are methyl groups.

[0073] Embodiment 8. The catalyst compound of any of embodiments 1-7, wherein 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 l,5,6,7,8,9-hexahydrocyclohepta[f]inden-l-ide.

[0074] Embodiment 9. A catalyst system comprising a catalyst compound represented by any of the following formulas:

[0075] Embodiment 10. A catalyst system of embodiment 9 further comprising an activator.

[0076] Embodiment 11. The catalyst system of embodiment 10 where activator comprises at least one of aluminoxane or salts of non-coordinating (NCA) anions.

[0077] Embodiment 12. The catalyst system of embodiment 11, wherein the salts of NCA ions 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 the charge d-; and d is an integer from 1 to 3.

[0078] Embodiment 13. The catalyst system of any of embodiments 11 or 12, wherein the NCA activator is represented by the formula: (Z)d+ (Ad-) wherein Ad- is a non-coordinating anion having a charge d-; d is an integer from 1 to 3, and Z is a reducible Lewis acid representedby 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.

[0079] Embodiment 14. The catalyst system of embodiment 11 where aluminoxane activator is present in ratios of greater than 1: 100 relative to metal.

[0080] Embodiment 15. The catalyst system of any of embodiments 9-14, further comprising a support material.

[0081] Embodiment 16. The catalyst system of embodiment 15, wherein the support material is selected from the group consisting of Al₂O₃, ZrO₂, SiO₂, SiO₂ / Al₂O₃, SiO₂ / TiO₂, silica clay, silicon oxide / clay, and combinations thereof.

[0082] Embodiment 17. A method comprising: introducing one or more of a C2 to C20 olefin monomer, and a catalyst system of any one of embodiments 9-16, 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 an alpha olefin polymer or copolymer.

[0083] Embodiment 18. The method of embodiment 17 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 -m ethyl- 1 -pentene, vinylcyclobutane, 1 -heptene, 1 -octene, 1 -decene, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene, norbornene, vinylnorbornene, ethylidine norbomene, and combinations thereof.

[0084] Embodiment 19. The method of any of embodiments 17 or 18, wherein the olefin polymer or copolymer has a Mw value of 1,000 to 1,000,000 g / mol, such as from 5,000 to 500,000 such as from 10,000 to 250,000 as measured by gel permeation chromatography.

[0085] Embodiment 20. The method of any of embodiments 17-19, wherein the alpha olefin polymer or copolymer has a Mw distribution with poly dispersity index less than 10.

[0086] Embodiment 21. The method of any one of embodiments 17 to 20, wherein the alpha olefin monomer comprises propylene.

[0087] Embodiment 22. The method of any of embodiments 17 to 21, wherein the alpha olefin polymer or copolymer has a melting point of greater than 120°C.

[0088] Embodiment 23. The method of any of embodiments 17 to 22, wherein the alpha olefin copolymer comprises a comonomer content of 0.01 - 99.99 wt.%.

[0089] To facilitate a better understanding of the present invention, the following examples of certain aspects of some embodiments are given. In no way should the following examples be read to limit, or define, the entire scope of the disclosure.Example 1

[0090] In this example, synthetic procedures that were used to prepare embodiments of the julolidine-based catalysts (i.e., 11-18) discussed above. Each of these synthetic procedures include at least proton Nuclear Magnetic Resonance (1H NMR) spectrum characterization data collected using a 400 megahertz (MHz) spectrometer in the indicated deuterated solvent.Synthesis of Catalyst II

[0091] To begin synthesis of II, a precursor chemical 9-(T etram ethyldi oxaborolanyl)- 1,1,7,7-tetramethyljulolidine as in Structure 2A was prepared.Structure 2A

[0092] Stirring a mixture of 1,1,7,7-tetramethyljulolidine (10.0096 g, 43.6 mmol), bis(pinacolato)diboron (11.3918 g, 44.9 mmol, 1.03 equivalent), (1,5-cyclooctadiene)(methoxy)iridium(I) dimer (291.7 mg, 440 pmol, 1 mol%), and 3,4,7,8-tetram ethyl- 1,10-phenanthroline (209.5 mg, 887 pmol, 2 mol%) in tetrahydrofuran (40 mL) was sealed in a pressure flask and heated to 90°C for 2 days. The reaction mixture was allowed to cool to room temperature and sit for approximately 7 hours. The crystalline precipitate was collected, washed with diethyl ether, and concentrated under high vacuum to afford a fraction of the product as a tan, crystalline solid (7.9940 g). The decantate and diethyl ether washes were mixed with additional diethyl ether (50mL) and placed in a freezer to facilitate product precipitation. The resulting precipitate was filtered over a plastic, fritted funnel, and washed with diethyl ether (20mL) and isohexanes (2 x 20mL). The filtered solid was collected and concentrated under high vacuum to afford another fraction of product as a light brown solid (3.3489 g; total yield 11.3429 g, 73%) to yield 7-(l,l,7,7-Tetramethyljulolid-9-yl)-2-methylindene as in Structure 2A.

[0093] The1H NMR spectrum of Structure 2A was (400 MHz, C6D6) 6 8.06 (s, 2H), 2.89-2.81 (m, 4H), 1.53-1.46 (m, 4H), 1.20 (s, 12H), 1.19 (s, 12H).

[0094] Next, 7-(l,l,7,7-Tetramethyljulolid-9-yl)-2-methylindene as in Structure 3 was prepared.Structure 3

[0095] Stirring mixture of 7-bromo-2-m ethylindene (0.5065 g, 2.42 mmol), 9-(tetramethyldioxaborolanyl)julolidine (0.9117 g, 2.57 mmol, 1.06 equivalent), potassium carbonate (1.0885 g, 7.88 mmol, 3.25 equivalent), bis(dibenzylideneacetone)palladium (31.1 mg, 54.1 pmol, 2 mol%), and l,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (52.3 mg, 179 pmol, 7 mol%) in tetrahydrofuran (50 mL) and water (10 mL) in a flask equipped with a reflux condenser was degassed and then left under Schlenk nitrogen. The mixture was stirred and heated to reflux overnight. The reaction was allowed to cool to room temperature. The reaction was partially concentrated in vacuo to remove the tetrahydrofuran. The residue was partitioned between dichloromethane (50 mL) and water (50 mL). The organic layer was extracted. The aqueous phase was further extracted with dichloromethane (2 x 50mL). The combined dichloromethane extracts were dried over anhydrous magnesium sulfate and filtered over a thin pad of silica. The filtrate was concentrated in vacuo to give an off-white foam that collapsed into a semi-solid. The crude was purified by silica gel column chromatography to afford the product as an expansive white foam (0.4751 g, 54% yield).

[0096] The1H NMR spectrum of Structure 3 was (400 MHz, CeDe) 8 7.44-7.33 (m, 4H), 7.27 (dd, 1H, J = 7.1, 1.4 Hz), 6.48 (q, 1H, J = 1.5 Hz), 3.34 (s, 2H), 2.96-2.87 (m, 4H), 1.86 (d, 3H, J = 1.5 Hz), 1.70-1.60 (m, 4H), 1.24 (s, 12H).

[0097] Next, lithium 2-methyl-4-(l, l,7,7-tetramethyljulolid-9-yl)indenide as in Structure 4 was prepared.Structure 4

[0098] To a precooled, stirring solution of 7-(l,l,7,7-tetramethyljulohd-9-yl)-2-methylindene (0.4751 g, 1.33 mmol) in diethyl ether (30 mL), n-butyllithium (0.50 mL, 2.71 M in hexanes, 1.4 mmol, 1 equivalent) was added. The reaction was stirred at room temperature overnight. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was washed with pentane (2 ^ 10 mL) and filtered over a plastic, fritted funnel. The filtered solid was collected and concentrated under high vacuum to afford the product as a pale yellow solid, containing pentane (0.27 equivalent) (0.4239 g, 83% yield).

[0099] The 'H NMR spectrum of Structure 4 was (400 MHz, THF- s) 67.47 (s, 2H), 7.13 (ddd, 1H, J = 6.6, 2.3, 0.8 Hz), 6.52-6.45 (m, 2H), 6.01 (d, 1H, J = 2.1 Hz), 5.81 (d, 1H, J = 2.1 Hz), 3.13-3.07 (m, 4H), 2.37 (s, 3H), 1.85-1.77 (m, 4H), 1.33 (s, 12H).

[0100] Next, dimethyl(4-(l,l,7,7-tetramethyljulolid-9-yl)-2-methylindenyl) (tetramethylcyclopentadienyl)-silane as in Structure 4 was prepared.Structure 5

[0101] To a precooled, stirring solution of dimethyl(tetramethylcyclopentadienyl)silyl trifluoromethanesulfonate (0.3735 g, 1.14 mmol) in diethyl ether (20 mL), a suspension of lithium 2-methyl-4-(l,l,7,7-tetramethyljulolid-9-yl)indenide (0.4239 g, 1.17 mmol, 1.03 equivalent) in diethyl ether (10 mL) was added. The reaction was stirred at room temperature overnight. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (20 mL, then 2 x 10 mL) and filtered over. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a white foam, containing dichloromethane (0.24 equivalent) (0.6288 g, 99% yield).

[0102] The 'H NMR spectrum of Structure 5 was (400 MHz, CeDe) 8 7.58-7.53 (m, 3H), 7.48-7.44 (m, 1H), 7.27 (t, 1H, J = 7.6 Hz), 7.12 (s, 1H), 3.69 (br s, 1H), 3.23 (br s, 1H), 2.97-2.91 (m, 4H), 2.09 (s, 3H), 1.97 (s, 3H), 1.90 (s, 3H), 1.83 (s, 6H), 1.70-1.64 (m, 4H), 1.28 (s, 6H), 1.27 (s, 6H), -0.16 (s, 3H), -0.20 (s, 3H).

[0103] Next, dimethylsilyl (4-(l,l,7,7-tetramethyljulolidyl)-2-methylindenyl) (tetramethylcyclopentadienyl) zirconium dichloride, catalyst II of Structure 6 was prepared.Structure 6

[0104] To a precooled, stirring solution of dimethyl(4-(l,l,7,7-tetramethyljulolid-9-yl)-2-methylindenyl)(tetramethylcyclopentadienyl)silane (0.6288 g, 1.13 mmol) in diethyl ether (30 mL), n-butyllithium (0.84 mL, 2.71 M in hexanes, 2.3 mmol, 2 equivalent) was added. The reaction was stirred at room temperature for 1 hour. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was washed with pentane and filtered over a plastic, fritted funnel. The filtered solid was collected and concentrated under high vacuum to afford the intermediate as a yellow solid, containing diethyl ether (0.53 equivalent) and pentane (0.35 equivalent) (0.5491 g). Diethyl ether (30 mL) was added to the solid, and the mixture was cooled (-35°C). To this precooled, stirring mixture, zirconium chloride (208.1 mg, 893 μmol, 1 equivalent) and toluene (2 mL) were added. The reaction was stirred at room temperature overnight. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (40 mL, then 2 x 10 mL) and filtered over Celite. The combined di chloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum. The resulting residue was stirred in pentane (10 mL). The resulting suspension was filtered over a plastic, fritted funnel. The filtered solid was collected and concentrated under high vacuum. The residue was stirred in diethyl ether (5 mL). The resulting suspension was filtered over a plastic, fritted funnel. The filtered solid was collected and concentrated under high vacuum to afford the product as an orange solid, containing diethyl ether (0.18 equivalent) (0.1269 g, 16% yield).

[0105] The1H NMR spectrum of Structure 6 was (400 MHz, CD2CI2) 8 7.49 (d, 1H, J = 8.8 Hz), 7.39 (s, 2H), 7.20 (dd, 1H, J = 7.1, 0.8 Hz), 7.03-6.97 (m, 2H), 3.22-3.12 (m, 4H), 2.28 (s, 3H), 2.08 (s, 3H), 2.00 (s, 3H), 1.91 (s, 3H), 1.89 (s, 3H), 1.83-1.76 (m, 4H), 1.40 (s, 6H), 1.26 (s, 6H), 1.21 (s, 3H), 1.11 (s, 3H).Synthesis of Catalyst 12

[0106] To begin synthesis of 12, a precursor chemical 8-(l,l,7,7-Tetramethyljulolid-9-yl)-6-methyl-l,2,3,5-tetrahydro-s-indacene of Structure 7 was prepared.Structure 7

[0107] A mixture of 8-bromo-6-methyl-l,2,3,5-tetrahydro-s-indacene (1.9950 g, 8.01 mmol), 9-(tetramethyldioxaborolanyl)-l,l,7,7-tetramethyljulolidine (2.8455 g, 8.01 mmol, 1 equivalent), potassium carbonate (2.4939 g, 18.0 mmol, 2.25 equivalent), bis(dibenzylideneacetone)palladium (96.0 mg, 167 pmol, 2 mol%), and l,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phospha-adamantane (147.6 mg, 505 pmol, 6 mol%) in tetrahydrofuran (50 mL) and water (10 mL) was stirred under nitrogen. The mixture was degassed on the Schlenk line. The mixture was then heated to reflux overnight. The reaction was allowed to cool to room temperature. The reaction was partially concentrated, to remove the tetrahydrofuran, in vacuo, and the residue was partitioned between dichloromethane (50 mL) and water (50 mL). The dichloromethane extract was collected, and the aqueous phase was extracted further with dichloromethane (20 mL). The combined dichloromethane extracts were concentrated in vacuo. Diethyl ether (lOmL) was added to the residue, and the mixture was stirred and then cooled in a freezer. The resulting suspension was filtered over a plastic, fritted funnel, washing with additional diethyl ether (10 mL) and isohexanes (10 mL). The filtered solid was collected and concentrated under high vacuum to afford the product as a tan solid (2.1816 g, 68% yield).

[0108] The 'H NMR spectrum of Structure 7 was (400 MHz, C6D6) 6 7.28 (s, 2H), 7.20 (s, 1H), 6.52 (q, 1H, J = 1.5 Hz), 3.29 (s, 2H), 3.03 (t, 2H, J = 7.2 Hz), 2.96 (t, 2H, J = 7.3 Hz), 2.94-2.88 (m, 4H), 1.95 (pent, 2H, J = 7.4 Hz), 1.89 (d, 3H, J = 1.5 Hz), 1.71-1.64 (m, 4H), 1.25 (s, 12H).

[0109] Next, lithium 4-(l,l,7,7-tetramethyljulolid-9-yl)-2-methyl-l,5,6,7-tetrahydro-s-indacenide as in Structure 8 was prepared.Structure 8

[0110] To a precooled, stirring solution of 8-(l,l,7,7-tetramethyljulolid-9-yl)-6-methyl-1,2,3,5-tetrahydro-s-indacene (0.2435 g, 612 pmol) in diethyl ether (10 mL), n-butyllithium (0.23 mL, 2.71 M in hexane, 0.62 mmol, 1 equivalent) was added. The reaction was stirred at room temperature for 1 hour. The reaction was filtered over a plastic, fritted funnel. The filtered solid was washed with additional diethyl ether (5 mL). The filtered solid was collected and concentrated under high vacuum to afford the product, containing diethyl ether (0.25 equivalent) (0.2181 g, 95% yield).

[0111] The 'H NMR spectrum of Structure 8 was (400 MHz, THF- s) 67.34 (s, 2H), 7.01 (s, 1H), 5.78 (s, 1H), 5.69 (s, 1H), 3.14-3.06 (m, 4H), 2.93-2.80 (m, 4H), 2.31 (s, 3H), 1.89 (pent, 2H, J = 7.0 Hz), 1.84-1.78 (m, 4H), 1.31 (s, 12H).

[0112] Next dimethyl(4-(l,l,7,7-tetramethyljulolid-9-yl)-2-methyl-l,5,6,7-tetrahydro-s-indacenyl)(tetra-methylcyclopentadienyl)silane as in Structure 9 was prepared.Structure 9

[0113] To a stirring solution of dimethyl(tetramethylcyclopentadienyl)silyl trifluoromethanesulfonate (0.1712 g, 521 pmol, 1.01 equivalent) in diethyl ether (5 mL), a suspension of lithium 4-(l,l,7,7-tetramethyljulolid-9-yl)-2-methyl-l,5,6,7-tetrahydro-s-indacenide (0.2181 g, 517 pmol,) in diethyl ether (5 mL) was added, washing with diethyl ether (5 mL). The reaction was stirred at room temperature for 3 hours. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (20 mL, then 2 x 10 mL) and filtered over Celite. The combined pentane extracts wereconcentrated under a stream of nitrogen and then under high vacuum to afford the product as a white foam (0.2846 g, 95% yield).

[0114] The1H NMR spectrum of Structure 9 was (400 MHz, CeDe) 6 7.45 (s, 1H), 7.43 (s, 2H), 6.97-6.94 (m, 1H), 3.72 (s, 1H), 3.30 (s, 1H), 3.17-2.98 (m, 4H), 2.98-2.90 (m, 4H), 2.08 (s, 3H), 2.04-1.87 (m, 8H), 1.84 (s, 6H), 1.74-1.65 (m, 4H), 1.29 (s, 12H), -0.11 (s, 3H), -0.17 (s, 3H).

[0115] Next, dilithium dimethyl(4-(l, 1,7, 7-tetramethyljulolid-9-yl)-2-methyl-l, 5,6,7-tetrahydro-s-indacenidyl)-(tetramethylcyclopentadienidyl)silane as in Structure 10 was prepared.Structure 10

[0116] To a precooled, stirring solution of dimethyl(4-(l,l,7,7-tetramethyljulolid-9-yl)-2-methyl-l,5,6,7-tetrahydro-s-indacenyl)(tetramethylcyclopentadienyl)silane (0.2846 g, 494 pmol) in diethyl ether (20 mL), n-butyllithium (0.37 mL, 2.71M in hexanes, 1.0 mmol, 2 equivalent) was added. The reaction was stirred at room temperature for 30 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in pentane (10 mL). The resulting suspension was filtered over a plastic, fritted funnel. The filtered solid was washed with additional pentane (5 mL). The filtered solid was collected and concentrated under high vacuum to afford the product as a yellow solid, containing pentane (0.46 equivalent) and diethyl ether (1.05 equivalent) (0.2755 g, 79% yield).

[0117] The ‘HNMR spectrum of Structure 10 was (400 MHz, THF-ds) 67.39 (s, 1H), 7.27 (s, 2H), 5.89 (s, 1H), 3.13-3.04 (m, 4H), 2.84 (t, 2H, J = 7.0 Hz), 2.36 (s, 3H), 2.13 (s, 6H), 1.91 (s, 6H), 1.86 (pent, 2H, J = 7.0 Hz), 1.84-1.78 (m, 4H), 1.29 (s, 12H), 0.58 (s, 6H).

[0118] Next, dimethylsilyl (4-(l,l,7,7-tetramethyljulolid-9-yl)-2-methyl-l,5,6,7-tetrahydro-s-indacenyl) (tetram ethylcyclopentadienyl) zirconium di chloride, catalyst 12 of Structure 11 was prepared.Structure 11

[0119] To a precooled, stirring solution of lithium dimethyl(4-(l,l,7,7-tetramethyljulolid-9-yl)-2-methyl-l,5,6,7-tetrahydro-s-indacenidyl)(tetramethylcyclopentadienidyl)silane (0.2755 g, 397 pmol) in diethyl ether (20 mL), zirconium chloride (92.4 mg, 397 pmol, 1.01 equivalent) was added, washing with toluene (3 mL). The reaction was stirred at room temperature overnight. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with di chloromethane (3 x 10mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum. The di chloromethane extract was stirred in pentane (3mL). The resulting suspension was filtered over a plastic, fritted funnel. The filtered solid was washed with additional pentane (2mL). The pentane-washed solid was collected and concentrated under high vacuum to afford the product as an orange solid, containing pentane (0.54 equivalent) (0.2054 g, 67% yield).

[0120] The1H NMR spectrum of Structure 11 was (400 MHz, CD2CI2) 6 7.30 (br s, 3H), 6.79 (s, 1H), 3.19-3.04 (m, 5H), 2.97-2.84 (m, 2H), 2.82-2.72 (m, 1H), 2.23 (s, 3H), 2.10-1.84 (m and 4 s, 18H), 1.83-1.76 (m, 4H), 1.35 (s, 6H), 1.27 (s, 6H), 1.20 (s, 3H), 1.08 (s, 3H).Catalyst 13

[0121] To begin synthesis of catalyst 13, the chemical as in Structure 12 was prepared.Structure 12

[0122] 4-bromo-2,2,6-tnmethyl-l,2,3,5-tetrahydro-s-indacene (0.90 g, 3.25 mmol) 9-(tetramethyldioxaborolanyl)julolidine (1.15 g, 3.25 mmol), potassium carbonate (1.01 g, 7.31 mmol), bis(dibenzylideneacetone)palladium (37.3 mg, 2 mol%), and l,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (56.9 mg, 6 mol%) were placed in 30 mL vial equipped with a septum. Tetrahydrofuran (12 mL) and degassed water (3 mL) were added. The reaction was stirred and heated to 75°C overnight. After 18 hours, the reaction mixture was concentrated in vacuo. The residue was diluted with methylene chloride (20 mL) and water (10 mL). The organic layer was separated, and aqueous layer was further extracted with 20 mL of methylene chloride. The combined organic layers were washed with water (2 x 20 mL) and brine (1 x 20 mL), dried over MgSO4, filtered and concentrated. The mixture was triturated with 10 mL of di ethylether. The insoluble material was collected and dried in vacuo. The diethyl ether fraction was concentrated to afford yellow solid. The solid was washed with acetone (5 mL) and dried in vacuo. Both fractions were spectroscopically pure for a combined yield of 73.1%.

[0123] The1H NMR spectrum of Structure 12 was (400 MHz, Chloroform-d) 8 7.10 (s, 2H), 7.03 (s, 1H), 6.48 (s, 1H), 3.27 (s, 2H), 3.18 (s, 4H), 2.80 (s, 2H), 2.73 (s, 2H), 2.12 (s, 3H), 1.85 (s, 4H), 1.33 (s, 12H), 1.16 (s, 6H).

[0124] Next the chemical of Structure 13 was prepared.

[0125] nBuLi (1.0 mL of 2.5 M solution) was slowly added to a stirring, pre-cooled diethylether solution of 4,4,10,10-tetramethyl-7-(2,2,6-trimethyl-3,7-dihydro-lH-s-indacen-4-yl)-l-azatricyclo[7.3.1.05,13]trideca-5(13),6,8-triene (1.0 g, 2.4 mmol) prepared in the previous step. The reaction mixture was allowed to warm up to room temperature and was stirred for 1 hour. After 1 hour, the solution is dark green. Solvent was removed in vacuo, and the residue was triturated with pentane. The solution was then filtered off to leave a white powder, which was washed with additional 2 x 10 mL of pentane and dried in vacuo. The 'H NMR spectrum of Structure 13 was (400 MHz, THF-d8) 67.36 (s, 2H), 6.99 (s, 1H), 5.81 (s, 1H), 5.71 (s, 1H), 3.13 (m, 4H), 2.77 (s, 2H), 2.72 (s, 2H), 2.34 (s, 3H), 1.85 (m, 4H), 1.34 (s, 12H), 1.12 (s, 6H).

[0126] Next the chemical of Structure 14 was prepared.Structure 14

[0127] Solid [2,6,6-trimethyl-4-(4,4,10,10-tetramethyl-l-azatricyclo[7.3.1.05,13]trideca- 5(13),6,8-trien-7-yl)-5,7-dihydro-lH-s-indacen-l-yl]lithium (0.94 g, 2.2 mmol) was slowly added to a stirring, pre-cooled solution of Me4CpSiMe2OTf (0.70 g, 2.1 mmol) in di ethylether. The reaction mixture was allowed to warm up to room temperature and was stirred for 1 hour. After 1 hour, solvent was removed in vacuo, and the residue was extracted with pentane (2 x 10 mL) and filtered over celite. Solvent removal afforded spectroscopically pure white foam in 93% yield.

[0128] The1H NMR spectrum of Structure 14 was (400 MHz, Benzene-d6) 67.43 (s, 2H), 7.40 (s, 1H), 6.97 (s, 1H), 3.71 (s, 1H), 3.28 (s, 1H), 2.96 (m, 6H), 2.10 (s, 3H), 2.00 (s, 3H), 1.94 (s, 3H), 1.83 (s, 6H), 1.67 (m, 4H), 1.29 (d, 12H), 1.21 (m, 2H), 1.11 (d, 6H), -0.09 (s, 3H), -0.14 (s, 3H).

[0129] Next the chemical of Structure 15 was prepared.

[0130] nBuLi (1.7 mL of 2.5 M solution) was slowly added to a pre-cooled (-35°C) solution of dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)-[2,6,6-trimethyl-4-(4,4,10,10-tetramethyl-l-azatricyclo[7.3.1.05,13]trideca-5,7,9(13)-trien-7-yl)-5,7-dihydro-lH-s-indacen-l-yl]silane (1.2 g, 2.0 mmol) in diethylether. The reaction mixture was allowed to warm up to room temperature and was stirred overnight. After 18 hours, the bright yellow mixture was concentrated in vacuo to give yellow solids. The solids were washed with pentane (2 x 20 mL),filtered over plastic frit, washed with additional pentane and dried in vacuo to afford spectroscopically pure complex dilithium complex.

[0131] The ‘HNMR spectrum of Structure 15 was (400 MHz, THF-d8) 67.38 (s, 1H), 7.28 (s, 2H), 5.90 (s, 1H), 3.11 (m, 4H), 2.72 (m, 4H), 2.38 (s, 3H), 2.18 (s, 6H), 1.95 (s, 6H), 1.84 (m, 4H), 1.33 (s, 12H), 1.12 (s, 6H), 0.63 (s, 6H).

[0132] Next, catalyst 13 of Structure 16 was prepared.Structure 16

[0133] ZrCh (0.31 g, 1.3 mmol) was placed in ca 25 mL of diethylether and was cooled to -30°C. Once cold, solid dilithium complex (0.89 g, 1.3 mmol) prepared in the last step was added. The mixture was allowed to warm up to room temperature and was stirred overnight. After 18 hours, the mixture was concentrated in vacuo to afford orange residue. The residue was extracted with toluene (3 x 10 mL), filtered over celite and concentrated. Addition of 20 mL of pentane resulted in precipitation of orange solid, which was collected on a filter frit and dried in vacuo to afford spectroscopically pure product in 76% yield isolated with about 0.2 equivalent of residual toluene.

[0134] The 'H NMR spectrum of Structure 16 was (400 MHz, Methylene Chloride-d2) 6 7.33 (m, 3H), 6.84 (s, 1H), 3.20 (m, 4H), 3.00 (s, 1H), 2.82 (d, 1H), 2.74 (d, 1H), 2.57 (d, 1H), 2.26 (d, 3H), 2.08 (s, 3H), 2.02 (s, 3H), 1.94 (s, 3H), 1.93 (s, 3H), 1.84 (m, 4H), 1.40 (s, 6H), 1.30 (s, 6H), 1.24 (two singlets, 6H), 1.11 (s, 3H), 1.00 (s, 3H).Catalyst 14

[0135] To begin synthesis of catalyst 14, the chemical of Structure 17 was prepared.Structure 17

[0136] 8-bromo-2,5,5,7,7-pentamethyl-l,6-dihydro-s-indacene (1.00 g, 3.28 mmol) 9-(tetramethyldioxaborolanyl)julolidine (1.15 g, 3.25 mmol), potassium carbonate (1.01 g, 7.31 mmol), bis(dibenzylideneacetone)palladium (37.3 mg, 2 mol%), and l,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (56.9 mg, 6 mol%) were placed in 30 mL vial equipped with a septum. Tetrahydrofuran (12 mL) and degassed water (3 mL) were added. The reaction was stirred and heated to 75°C overnight. After 18 hours, the reaction mixture was concentrated in vacuo. The residue was diluted with methylene chloride (20 mL) and water (10 mL). The organic layer was separated, and aqueous layer was further extracted with 20 mL of methylene chloride. The combined organic layers were washed with water (2 x 20 mL) and brine (1 x 20 mL), dried over MgSO4, filtered and concentrated. The mixture was triturated with 10 mL of di ethylether. The insoluble material was collected and dried in vacuo. The diethyl ether fraction was concentrated to afford yellow solid. The solid was washed with acetone (5 mL) and dried in vacuo. Both fractions were spectroscopically pure for a combined yield of 73.1%.

[0137] The 'H NMR spectrum of Structure 17 was (400 MHz, Chloroform-d) 6 7.10 (s, 2H), 7.03 (s, 1H), 6.48 (s, 1H), 3.27 (s, 2H), 3.18 (s, 4H), 2.80 (s, 2H), 2.73 (s, 2H), 2.12 (s, 3H), 1.85 (s, 4H), 1.33 (s, 12H), 1.16 (s, 6H).

[0138] Next, the chemical of Structure 18 was prepared.Structure 18

[0139] nBuLi (0.9 mL of 2.5 M solution) was slowly added to a stirring, pre-cooled diethylether solution of 4,4,10,10-tetramethyl-7-(2,5,5,7,7-pentamethyl-l,6-dihydro-s-indacen-4-yl)-l-azatricyclo[7.3.1.05,13]trideca-5(13),6,8-triene (0.97 g, 2.1 mmol). The reaction mixture was allowed to warm up to room temperature. After 1 hour the mixture solvent was removed in vacuo, and the residue was triturated with pentane. The solution was filtered off to leave white powder, which was washed with 2 x 10 mL of pentane and dried in vacuo to afford spectroscopically pure product in 91% yield.

[0140] The 'H NMR spectrum of Structure 18 was (400 MHz, THF-d8) 66.99 (s, 3H), 5.71 (m, 1H), 5.25 (m, 1H), 3.17 - 3.12 (m, 4H), 2.26 (s, 3H), 1.85 (m, 4H), 1.82 (s, 2H), 1.35 (s, 6H), 1.29 (overlapping s, 12H), 1.14 (s, 6H).

[0141] Next, the chemical of Structure 19 was prepared.Structure 19

[0142] Solid [2,5,5,7,7-pentamethyl-4-(4,4,10,10-tetramethyl-l-azatricyclo[7.3.1.05,13] trideca-5(13),6,8-trien-7-yl)-l,6-dihydro-s-indacen-l-yl]lithium (0.89 g, 1.9 mmol) was slowly added to a stirring, pre-cooled solution of Me4CpSiMe2OTf (0.62 g, 1.9 mmol) in diethylether. The reaction mixture was allowed to warm up to room temperature and was stirred for 1 hour. After 1 hour, solvent was removed in vacuo, and the residue was extracted with pentane (2 x 10 mL) and filtered over celite. Solvent removal afforded spectroscopically pure white foam in 96% yield.

[0143] The1H NMR spectrum of Structure 19 was (400 MHz, Benzene-d6) 67.38 (s, 1H), 7.25 (s, 1H), 6.55 (s, 1H), 3.62 (s, 1H), 3.20 (s, 1H), 2.93 (m, 4H), 2.01 (m, 2H), 2.00 (m, 3H), 1.96 (s, 3H), 1.93 (s, 3H), 1.83 (s, 6H), 1.69 (m, 4H), 1.52 (s, 3H), 1.49 (s, 3H), 1.41 (s, 3H), 1.39 (s, 3H), 1.31 (s, 3H), 1.29 (s, 3H), 1.26 (s, 3H), 1.25 (s, 3H), -0.08 (s, 3H), -0.15 (s, 3H).

[0144] Next, the chemical of Structure 20 was prepared.

[0145] nBuLi (1.5 mL of 2.5 M solution) was slowly added to a pre-cooled (-35°C) solution of dimethyl-[2,5,5,7,7-pentamethyl-4-(4,4,10,10-tetramethyl-l-azatricyclo[7.3.1.05,13]trideca-5,7,9(13)-trien-7-yl)-l,6-dihydro-s-indacen-l-yl]-(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane (1.2 g, 1.9 mmol) in diethylether. The reaction mixture was allowed to warm up toroom temperature and was stirred for 1 hour. After 1 hour, the bright yellow mixture was concentrated in vacuo to give yellow solids. Pentane (ca 20 mL) was added, the resulting yellow solids were stirred for 5 minutes, filtered over plastic frit, washed with additional pentane and dried in vacuo to afford spectroscopically pure product with 0.41 equivalent Et2O and 0.36 equivalent residual pentane in 59% yield.

[0146] The 'H NMR spectrum of Structure 20 was (400 MHz, THF-d8) 87.05 (s, 1H), 6.92 (s, 2H), 5.33 (s, 1H), 3.13 (m, 4H), 2.30 (s, 3H), 2.21 (s, 6H), 1.99 (s, 6H), 1.85 (m, 4H), 1.78 (m, 2H), 1.30 - 1.25 (3 singlets, 18H), 1.11 (s, 6H), 0.95 - 0.91 (m, 2H), 0.63 (s, 6H).

[0147] Next, catalyst 14 of Structure 21 was prepared.Structure 21

[0148] ZrCh (0.25 g, 1.1 mmol) was placed in ca 25 mL of diethylether and was cooled to -30°C. Once cold, solid dilithiated ligand prepared in the previous step (0.77 g, 1.1 mmol) was added. The mixture was allowed to warm up to room temperature and was stirred overnight. After 18 hours, the mixture was concentrated in vacuo to afford orange residue. The residue was extracted with toluene (3 x 10 mL), filtered over celite and concentrated. Addition of 20 mL of pentane resulted in precipitation of yellow solid, which was collected on a filter frit and dried in vacuo to afford pure product.

[0149] The1H NMR spectrum of Structure 21 (400 MHz, Methylene Chloride-d2) 6 7.45 (s, 1H), 7.22 (s, 1H), 6.81 (s, 1H), 6.37 (s, 1H), 3.18 (m, 4H), 2.21 (s, 3H), 2.04 (s, 3H), 1.98 (s, 3H), 1.97 (s, 3H), 1.95 (s, 3H), 1.87 (s, 2H), 1.82 (m, 4H), 1.36 (s, 3H), 1.29 - 1.26 (3 overlapping singlets, 9H), 1.26 - 1.23 (3 overlapping singlets, 9H), 1.19 (s, 3H), 1.19 (s, 3H), 1.10 (s, 3H).Catalyst 15

[0150] To begin synthesis of catalyst 15, the chemical of Structure 22 (1,1,7,7-Tetramethyl-9-(2-methyl-5,6,7,8-tetrahydro-U / -cyclopenta[Z»]naphthalen-4-yl)-2,3,6,7-tetrahydro-lH,5H-pyrido[3,2,l-ij]quinoline) was prepared.Structure 22

[0151] 4-Bromo-2-methyl-3,5,6,7,8,9-hexahydrocyclohepta[ / ]indene (0.60 g, 2.16 mmol), (9-(tetramethyldioxaborolanyl)-l,l,7,7-tetramethyljulolidine (0.810 g, 2.28 mmol), K2CO3 (0.693 g, 5.02 mmol), bis(dibenzylideneacetone)palladium(0) (66 mg, 0.114 mmol), l,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (100 mg, 0.342 mmol) and THF (25 mL) were added to a pressure-resistant flask followed by degassed water (3.5 mL). The flask was sealed and heated with vigorous stirring at 80°C for 14 hours. Then, the flask was cooled to the ambient temperature and the reaction volume was reduced to ca 3 mL and diluted with water (20 mL). The product was extracted into dichloromethane (3 x 20 mL) and the combined organic phase was dried over MgSCU and evaporated to give an orange oil. The resulting crude product was purified on Biotage automated column using silica gel and the mixture of CH2CI2 and w-hexane (gradient from 5:95 to 75:25, v:v, respectively) as an eluent. Yield: 0.564 g (60%).

[0152] The 'H NMR spectrum of Structure 22 was (400 MHz, CDCh) 67.02 (s, 1H), 6.98 (s, 2H), 6.49 (h, J= 1.6 Hz, 1H), 3.23 - 3.15 (m, 4H), 3.15 - 3.08 (m, 2H), 2.92 (t, J= 6.4 Hz, 2H), 2.60 (t, J = 6.3 Hz, 2H), 2.12 (d, J = 1.6 Hz, 3H), 1.92 - 1.71 (m, 8H), 1.34 (s, 12H).13C NMR (101 MHz, CDCh) 6 145.80, 143.12, 140.39, 139.39, 138.59, 135.47, 130.71, 130.35, 127.57, 126.76, 125.15, 119.07, 47.14, 42.83, 37.38, 32.52, 32.16, 32.05, 30.50, 28.17, 23.88, 23.27, 16.85.

[0153] Next the chemical of Structure 23 ((2-Methyl-4-(l,l,7,7-tetramethyl-2,3,6,7-tetrahydro-U / ,5J / -pyrido[3,2,l-ij]quinolin-9-yl)-5,6,7,8-tetrahydro-U / -cyclopenta[Z»] naphthalen-l-yl)lithium) was prepared.Structure 23

[0154] / / BuLi (1.03 mL, 1.6M, 1.65 mmol) was added to the solution of l,l,7,7-tetramethyl-9-(2-methyl-5,6,7,8-tetrahydro-U / -cyclopenta[Z»]naphthalen-4-yl)-2,3,6,7-tetrahydro-lH,5H-pyrido[3,2,l-ij]quinolone (564 mg, 1.37 mmol) in Et2O (10 mL) at -35°C under stirring. The resulting mixture was allowed to warm up to the ambient temperature. After stirring for 1 hour at ambient temperature, the volatiles were evaporated and / / -pentane (10 mL) was added A white solid product was collected on a filter disk, washed several times with w-pentane (20 mL) and dried in vacuo to give a product as an adduct with 1 equivalent of THF. Yield: 0.545 g (81%).

[0155] The *HNMR spectrum of Structure 23 was (400 MHz, THF- s) 67.13 (s, 2H), 6.94 (s, 1H), 5.65 (d, J= 2.2 Hz, 1H), 5.49 (d, J= 2.1 Hz, 1H), 3.71 - 3.61 (m, 4H), 3.23 - 3.04 (m, 4H), 2.87 (t, J= 6.4 Hz, 2H), 2.71 (t, J= 6.3 Hz, 2H), 2.29 (s, 3H), 1.92 - 1.83 (m, 4H), 1.81 (m, 4H), 1.77 (m, 2H), 1.67 (m, 2H), 1.33 (s, 12H).13C NMR (101 MHz, THF- s) 6 138.39, 131.49, 130.14, 129.23, 127.86, 127.57, 126.48, 125.72, 122.80, 119.46, 116.35, 91.75, 90.03, 67.27, 47.14, 38.05, 32.20, 31.81, 31.11, 28.23, 25.42, 24.50, 22.25, 15.64, 13.44.

[0156] Next the chemical of Structure 24 (9-(l-(Dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl)-2-methyl-5,6,7,8-tetrahydro-U / -cyclopenta[Z»]naphthalen-4-yl)-l,l,7,7-tetramethyl-2,3,6,7-tetrahydro-U / ,5J / -pyrido[3,2,l-ij]quinoline) was prepared.Structure 24

[0157] To a stirring solution of dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl trifluoromethanesulfonate (347 mg, 1.06 mmol) in diethyl ether (10 mL) was added a suspension of (2-methyl-4-(l,l,7,7-tetramethyl-2,3,6,7-tetrahydro-U / ,5J / -pyrido[3,2,l-ij]quinolin-9-yl)-5,6,7,8-tetrahydro-U / -cyclopenta[Z»]naphthalen-l-yl)lithium (544 mg, 1.11 mmol, adduct with 1 equivalent of THF) in diethyl ether (10 mL) at -35°C. The reaction was allowed to warm up to ambient temperature and stirred for 90 minutes. Then, the reaction was concentrated under a stream of nitrogen and the resulting residue was dried under vacuum. The product was extracted into / / -pentane (2 x 20 mL) and filtered through celite plug. Concentration under a stream of nitrogen and drying in vacuo afforded the product as a white foam. Yield: 612 mg (98%).

[0158] The 'H NMR spectrum of Structure 24 was (400 MHz, CDCh) 67.14 (s, 1H), 7.02 (d, J= 2.1 Hz, 1H), 6.97 (t, J= 2.1 Hz, 1H), 6.39 (d, J= 1.6 Hz, 1H), 3.61 (s, 1H), 3.33 (s, 1H),3.19 (t, J = 5.8 Hz, 4H), 2.91 (q, J = 6.1 Hz, 2H), 2.68 (q, J = 6.0 Hz, 2H), 2.19 (s, 3H), 2.11 (s, 3H), 2.05 (s, 3H), 1.95 - 1.80 (m, 10H), 1.77 (m, 4H), 1.35 (m, 12H), -0.19 (s, 3H), -0.22 (s, 3H).13C NMR (101 MHz, CDCh) 6 145.31, 142.67, 142.47, 139.22, 136.58, 136.53, 134.40, 133.14, 131.77, 131.55, 129.99, 129.91, 127.54, 126.73, 126.25, 126.08, 122.72, 47.17, 46.83, 37.46, 34.16, 32.47, 32.46, 32.12, 32.11, 32.04, 32.00, 30.66, 28.31, 23.95, 23.39, 22.38, 18.05, 14.92, 14.82, 14.10, 11.28, -5.29, -5.74.

[0159] Next catalyst 15 of Structure 25 (9-(l-(Dimethyl(2,3,4,5-tetramethyl cyclopentadienyl)silyl)-2-methyl-5,6,7,8-tetrahydro-17 -cyclopenta[Z»]naphthalen-4-yl)-l,l,7,7-tetramethyl-2,3,6,7-tetrahydro-U / ,5J / -pyrido[3,2,l-z / ]quinolone zirconium dichloride) was prepared.Structure 25

[0160] / / BuLi (1.36 mL, 1.6 M in hexane, 2.18 mmol) was added dropwise to a precooled solution (-30°C) of 9-(l-(dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl)-2-methyl-5,6,7,8-tetrahydro-U / -cyclopenta[Z»]naphthalen-4-yl)-l,l,7,7-tetramethyl-2,3,6,7-tetrahydro-U / ,5J / -pyrido[3,2,l-ij]quinoline (611 mg, 1.04 mmol) in Et2O (15 mL). The mixture was allowed to warm up to the ambient temperature under stirring over 1 hour. The volatiles were evaporated, and the resulting product was washed with / / -pentane (2 x 5 mL) to give a beige solid of the dilithium salt. It was dissolved in Et2O / THF (10:1 mL, v:v, respectively). The resulting solution was cooled back to -30°C before solid (Et2O)2ZrC14 (435 mg, 1.14 mmol) was added in small portions over 10 minutes. The mixture was stirred for 10 minutes at -30°C and then the reaction mixture was gradually warmed up to ambient temperature. Additional stirring for 1 hour, all volatiles were evaporated, and the product was extracted into CH2CI2 (15 mL). Filtration through a celite plug and evaporation of the solvent gave a dark orange oil. The desired product was extracted from this oil by washing with / / -pentane (2 x 5 mL). Evaporation of solvent and drying in vacuo gave an orange solid complex as an adduct with 2 equivalents of w-pentane. Yield: 230 mg (25%).

[0161] The 'H NMR. spectrum of Structure 25 was (400 MHz, CDCI3) 87.53 (d, J =2.0 Hz, 1H), 7.25 (s, 1H), 6.91 (d, = 2.0Hz, 1H), 6.70 (s, 1H), 3.24-3.17 (m, 4H), 2.99-2.54 (m, 4H),2.26 (s, 3H), 2.08 (s, 3H), 2.04 (s, 3H), 1.98 (s, 3H), 1.97 (s, 3H), 1.94 - 1.72 (m, 12H), 1.43 (s, 3H), 1.42 - 1.25 (m, 5H), 1.24 (s, 3H), 1.11 (s, 3H).13C NMR (101 MHz, CDCh) 6 139.81, 137.14, 136.10, 135.52, 135.23, 134.29, 133.60, 130.63, 129.59, 127.07, 126.45, 126.10, 126.00, 125.86, 125.53, 124.08, 121.60, 121.34, 93.64, 80.74, 47.19, 43.13, 37.51, 37.38, 32.70, 32.43, 32.20, 31.98, 31.79, 30.94, 27.73, 23.30, 22.46, 18.09, 15.81, 15.46, 12.58, 12.21, 3.25, 3.21.Catalyst 16

[0162] To begin synthesis of catalyst 16, the chemical of Structure 26 (1,1,7,7-Tetramethyl- 9-(2-methyl-l,5,6,7,8,9-hexahydrocyclohepta[ / ]inden-4-yl)-2,3,6,7-tetrahydro-U / ,5J / -pyrido [3,2, 1-ij] quinoline) was prepared.Structure 26

[0163] 4-Bromo-2-methyl-3,5,6,7,8,9-hexahydrocyclohepta[ / ]indene (0.60 g, 2.16 mmol), (9-(tetramethyldioxaborolanyl)-l,l,7,7-tetramethyljulolidine (0.769 g, 2.16 mmol), K2CO3 (0.658 g, 4.76 mmol), bis(dibenzylideneacetone)palladium(0) (62 mg, 0.108 mmol), 1, 3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (95 mg, 0.325 mmol) and THF (25 mL) were added to a pressure-resistant flask followed by degassed water (3.5 mL). The flask was sealed and heated with vigorous stirring at 80°C for 14 hours. Then, the flask was cooled to the ambient temperature and the reaction volume was reduced to ca 3 mL and diluted with water (20 mL). The product was extracted into dichloromethane (3 x 20 mL) and the combined organic phase was dried over MgSCU and evaporated to give an orange oil. The resulting crude product was purified by recrystallization from w-hexane. Yield: 0.675 g (73%).

[0164] The1H NMR spectrum of Structure 26 was (400 MHz, CDCh): 67.07 (s, 1H), 6.98 (s, 2H), 6.49 (s, 1H), 3.20 (t, J= 5.7 Hz, 4H), 3.14 (s, 2H), 2.96 - 2.89 (m, 2H), 2.77 - 2.70 (m, 2H), 2.12 (s, 3H), 1.89 (dd, J= 8.0, 3.9 Hz, 6H), 1.82 - 1.72 (m, 2H), 1.67 (p, J= 5.4 Hz, 2H), 1.34 (m, 12H).13C NMR (101 MHz, CDCh) 6 145.94, 143.02, 142.61, 140.61, 139.35, 138.23, 136.98, 130.21, 128.20, 126.85, 125.53, 119.31, 47.15, 43.42, 37.37, 37.12, 32.74, 32.49, 32.13, 31.16, 28.80, 28.64, 22.69, 16.82.

[0165] Next the chemical of Structure 27 ([2-Methyl-4-(3, 3,11,11 -tetramethyl- 1-azatricyclo[7.3.1.05,13]trideca-5(13),6,8-trien-7-yl)-3,5,6,7,8,9-hexahydrocyclohepta[f]inden-3-yl]lithium) was prepared.Structure 27

[0166] nBuLi (1.03 mL, 1.6 M, 1.65 mmol) was added to the solution of l,l,7,7-tetramethyl-9-(2-methyl-l,5,6,7,8,9-hexahydrocyclohepta[ / ]inden-4-yl)-2,3,6,7-tetrahydro-U / ,5J / -pyrido [3,2, 1-ij] quinoline (670 mg, 1.57 mmol) in Et20 (10 mL) at -40°C under stirring. The resulting mixture was allowed to warm up to ambient temperature to give an orange solution with a white precipitate. After stirring for 1 hour at ambient temperature, the volatiles were evaporated and / / -pentane (10 mL) was added A white solid product was collected on a filter disk, washed several times with / / -pentane (20 mL) and dried in vacuo. Yield: 0.577 g (85%).

[0167] The1H NMR spectrum of Structure 27 was (400 MHz, THF- s) 67.14 (s, 2H), 6.99 (s, 1H), 5.68 (d, J= 2.2 Hz, 1H), 5.50 (d, J= 2.1 Hz, 1H), 3.14 (t, J = 5.7 Hz, 4H), 2.96-2.80 (m, 2H), 2.80-2.63 (m, 2H), 2.29 (s, 3H), 1.85 (m, 5H), 1.80 - 1.61 (m, 6H), 1.35 (s, 5H), 1.33 (s, 6H).13C NMR (101 MHZ, THF-t / s) 6 138.45, 132.02, 130.84, 129.54, 129.17, 127.35, 126.95, 126.73, 125.37, 125.15, 117.18, 92.65, 90.98, 65.36, 47.13, 38.04, 32.85, 32.19, 31.82, 31.34, 30.85, 30.78, 15.61, 14.75.

[0168] Next the chemical of Structure 28 (9-(l-(Dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl)-2-methyl-l,5,6,7,8,9-hexahydrocyclohepta[ / ]inden-4-yl)-l,l,7,7-tetramethyl-2,3,6,7-tetrahydro-U / ,5J / -pyrido[3,2,l-z / ]quinolone) was prepared.Structure 28

[0169] To a stirring solution of dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl trifluoromethanesulfonate (417 mg, 1.27 mmol) in diethyl ether (10 mL) was added a suspension of 2-methyl-4-(3,3,ll,ll-tetramethyl-l-azatricyclo[7.3.1.05,13]trideca-5(13),6,8-trien-7-yl)-3,5,6,7,8,9-hexahydrocyclohepta[f]inden-3-yl]lithium (577 mg, 1.34 mmol) in diethyl ether (5 mL) at -35°C. The reaction was allowed to warm up to ambient temperature and stirred for 90 minutes. Then, the reaction was concentrated under a stream of nitrogen and the resulting residue was dried under vacuum. The product was extracted into / / -pentane (2 x 20 mL) and filtered through celite plug. Concentration under a stream of nitrogen and drying in vacuo afforded the product as a white foam. Yield: 753 mg (98%).

[0170] The1H NMR spectrum of Structure 28 was (400 MHz, CDCh): 67.20 (s, 1H), 7.02 (d, J= 2.0 Hz, 1H), 6.98 (d, J= 2.0 Hz, 1H), 6.42 (s, 1H), 3.65 (s, 1H), 3.34 (s, 1H), 3.29-3.09 (m, 4H), 3.09 - 2.81 (m, 2H), 2.72 (m, 2H), 2.21 (s, 3H), 2.12 (s, 3H), 2.05 (s, 4H), 1.99-1.74 (m, 15H), 1.50-1.20 (m, 12H), -0.16 (s, 3H), -0.20 (s, 3H).13C NMR (101 MHz, CDCh): 6 145.49, 142.84, 142.35, 139.19, 138.86, 137.76, 136.60, 136.51, 134.44, 129.97, 129.84, 128.20, 127.14, 126.58, 126.46, 122.68, 47.47, 47.20, 37.48, 37.38, 34.18, 32.71, 32.46, 32.44, 32.16, 32.15, 32.09, 31.21, 29.08, 28.87, 22.40, 17.99, 14.91, 14.85, 14.12, 11.32, 11.30, -5.28, -5.63.

[0171] Next the catalyst 16 of Structure 29 (9-(l-(Dimethyl(2,3,4,5-tetramethylcyclopentadienyl)silyl)-2-methyl-5,6,7,8,9-pentahydrocyclohepta[ / ]indenyl)-l,l,7,7-tetramethyl-2,3,6,7-tetrahydro-U / ,5J / -pyrido[3,2,l- / / ]quinolone zirconium dichloride) was prepared.Structure 29

[0172] / / BuLi (1.76 mL, 1.6 M in hexane, 2.82 mmol) was added dropwise to a precooled solution (-30°C) of9-(l-(dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silyl)-2-methyl-l,5,6,7,8,9-hexahydrocyclohepta[ / ]inden-4-yl)-l,l,7,7-tetramethyl-2,3,6,7-tetrahydro-U / ,5J / -pyrido[3,2,l-z / ]quinolone (810 mg, 1.34 mmol) in Et2O (15 mL). The mixture was allowed to warm up to the ambient temperature under stirring over 1 hour. The resulting white suspensionwas cooled back to -30°C before solid (Et2O)2ZrC14 (562 mg, 1.48 mmol) was added in small portions over 10 minutes. The mixture was stirred for 10 minutes at -30°C and then the reaction mixture was gradually warmed up to ambient temperature. Additional stirring for 1 hour gave a yellow precipitate. Volatiles were then evaporated and the product was extracted into CH2CI2 (15 mL). Filtration through a celite plug and evaporation of the solvent gave a dark orange oil which was suspended in / / -pentane (3 mL). The formed yellow precipitate was collected by filtration, washed with / / -pentane (3 mL) and dried in vacuo. Yield: 335 mg (33%).

[0173] The1H NMR spectrum of Structure 29 was (400 MHz, CDCh) 67.49 (s, 1H), 7.26 (s, 1H), 6.84 (s, 1H), 6.61 (s, 1H), 3.29 - 3.03 (m, 4H), 2.85-2.78 (m, 3H), 2.06 (s, 3H), 2.02 (s, 3H), 1.97 (s, 3H), 1.96 (s, 3H), 1.92-1.53 (m, 10H), 1.39 (s, 3H), 1.35-1.30 (m, 7H), 1.29 (s, 6H), 1.22 (s, 3H), 1.08 (s, 3H).13C NMR (101 MHz, CDCh): 6 142.60, 140.86, 139.80, 137.27, 135.54, 134.31, 133.66, 126.89, 126.76, 126.28, 125.95, 123.96, 121.95, 121.67, 93.77, 81.76, 77.23, 47.21, 47.16, 37.81, 37.43, 37.35, 34.14, 32.65, 32.39, 32.22, 32.03, 31.73, 31.26, 30.22, 29.02, 22.35, 18.08, 15.87, 15.47, 14.08, 12.57, 12.18, 3.18.Catalyst 17

[0174] To begin synthesis of catalyst 17, chlorodimethyl(2-methyl-4-(l, 1,7,7-tetramethyljulolid-9-yl)-l,5,6,7-tetrahydro-s-indacenyl)silane as in Structure 30 was prepared.Structure 30

[0175] To a stirring solution of dichlorodimethylsilane (1.40 mL, 11.6 mmol, 10.2 equivalent) in diethyl ether (20 mL), a suspension of lithium 4-(l,l,7,7-tetramethyljulolid-9-yl)-2-methyl-l,5,6,7-tetrahydro-s-indacenide (0.4856 g, 94.2% purity, 1.13 mmol) in diethyl ether (20 mL) was added. The reaction was stirred at room temperature overnight. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted dichloromethane and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a white foam (0.5097 g, 91% yield).

[0176] The1H NMR spectrum of Structure 30 was (400 MHz, C6D6) 6 7.39 (br s, 1H), 7.36 (s, 2H), 6.87 (dd, 1H, J = 2.2, 1.3 Hz), 3.44 (s, 1H), 3.03-2.93 (m, 4H), 2.92-2.86 (m, 4H), 2.13-2.09 (m, 3H), 1.91 (p, 2H, J = 7.3 Hz), 1.81-1.73 (m, 4H), 1.24 (s, 6H), 1.22 (s, 6H), 0.31 (s, 3H), 0.06 (s, 3H).

[0177] Next, dimethylbis(2-methyl-4-(l,l,7,7-tetramethyljulolid-9-yl)-l,5,6,7-tetrahydro-s-indacenyl)silane as in Structure 31 was prepared.Structure 31

[0178] To a precooled, stirring solution of chlorodimethyl(2-methyl-4-(l, 1,7,7-tetramethyljulolid-9-yl)-l,5,6,7-tetrahydro-s-indacenyl)silane (0.5097 g, 1.04 mmol) in dichloromethane (30 mL), silver(I) trifluoromethanesulfonate (0.2655 g, 1.03 mmol, 1 equivalent) was added, washing residual silver(I) trifluoromethanesulfoante into the reaction with additional dichloromethane (5 mL). The reaction was stirred at room temperature for 1 hour. The reaction was filtered over Celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give a dark green foam (0.5869 g; 0.0525 g set aside). The remaining foam was dissolved in diethyl ether (30 mL). Then, lithium 4-(l, 1,7,7-tetramethyljulolid-9-yl)-2-methyl-l,5,6,7-tetrahydro-s-indacenide (0.3691 g, 915 mmol, 1 equivalent) was added, washing with diethyl ether (10 mL). The reaction was stirred at room temperature for 30 minutes. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (2 x 20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to give an off-white foam (0.7625 g, 92.1% yield, mixture of isomers with unknown impurity).

[0179] The 'H NMR spectrum of Structure 31 was (400 MHz, C6D6) 67.61 (s, 2H), 7.47 (s, 8H), 7.34 (s, 2H), 7.01 (s, 2H), 6.99 (s, 2H), 3.94 (s, 2H), 3.92 (s, 2H), 3.18-2.88 (m, 32H), 2.12 (s, 6H), 2.04 (s, 6H), 2.00-1.88 (m, 8H), 1.75-1.65 (m, 16H), 1.33-1.28 (m, 48H), -0.03 (s, 3H), -0.09 (s, 6H), -0.16 (s, 3H).

[0180] Next, lithium dimethylbis(2-methyl-4-(l, 1,7, 7-tetramethyljulolid-9-yl)-l, 5,6,7-tetrahydro-s-indacenid-yl)silane as in Structure 32 was prepared.Structure 32

[0181] To a precooled, stirring solution of dimethylbis(2-methyl-4-(l, 1,7,7-tetramethyljulolid-9-yl)-l,5,6,7-tetrahydro-s-indacenyl)silane (0.7625 g, 896 mmol) in diethyl ether (30 mL), n-butyllithium (0.67 mL, 2.71 M in hexanes, 1.8 mmol, 2 equivalent) was added. The reaction was stirred at room temperature overnight. The reaction, a white suspension, was filtered over a plastic, fritted funnel, washing with pentane (lOmL). The white solid was collected and concentrated under high vacuum with stirring to afford the product as a pale yellow solid, containing diethyl ether (0.79 equivalent) (0.3616 g, 43% yield).

[0182] The 'H NMR spectrum of Structure 32 was (400 MHz, C4D8O) 87.52 (s, 2H), 7.28 (s, 4H), 5.92 (s, 2H), 3.13-3.05 (m, 8H), 2.90-2.81 (m, 8H), 2.38 (s, 6H), 1.93-1.76 (m, 12H), 1.29 (s, 24H), 0.75 (s, 6H).

[0183] Next, the catalyst structure of 17 having the chemical of Structure 33 was prepared.Structure 33

[0184] To a precooled, stirring solution of lithium dimethylbis(2-methyl-4-(l, 1,7,7-tetramethyljulolid-9-yl)-l,5,6,7-tetrahydro-s-indacenidyl)silane (361.6 mg, 392 mmol) in diethyl ether (30 mL), zirconium chloride (92.0 mg, 395 mmol, 1.01 equivalent) was added, washing the residual zirconium chloride into the reaction with toluene (2 mL). The reaction was stirred at room temperature overnight. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (440 mL, then 10 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to give an orange-red solid. The solid was stirred in pentane (5 mL). The resulting suspension was filtered over a plastic, fritted funnel, washing with additional pentane (5 mL). The filtered solid was collected and concentrated under high vacuum to give an orange solid (1.3:1 isomer ratio, 0.2849 g, 71% yield). Isomer enrichment: The pentane washed dichloromethane extract was stirred in diethyl ether (5 mL). The resulting suspension was filtered over a plastic, fritted funnel, washing with additional diethyl ether (5 mL). The diethyl ether washed solid was collected and concentrated under high vacuum to give an orange solid (2.3:1 isomer ratio). The diethyl ether extracts were placed in a freezer to facilitate precipitation. The diethyl ether and pentane washed di chloromethane extract was slowly stirred in minimal dichloromethane (1 mL). The resulting mixture was filtered overa plastic, fritted funnel, washing with minimal additional di chloromethane (0.5 mL). The filtered solid was collected and concentrated under high vacuum to afford a fraction of the product as an orange solid (0.1406 g, rac-enriched (7:1)). Solids precipitated from cold diethyl ether extract of the pentane-washed dichloromethane extract. The solids were collected and concentrated under high vacuum to afford a fraction of the product as an orange solid (0.0183 g, meso isomer).

[0185] The ’H NMR spectrum of Structure 33 was (400 MHz, CD2C12): rac 67.38 (s, 2H), 7.28 (br s, 4H), 6.70 (s, 2H), 3.23-3.05 (m, 10H), 3.01-2.76 (m, 6H), 2.21 (s, 6H), 2.16-2.03 (m, 2H), 1.98-1.83 (m, 2H), 1.81-1.70 (m, 8H), 1.301+1.298 (two s, 18H), 1.21 (s, 12H); meso 6 7.37 (s, 2H), 7.25 (br s, 4H), 6.56 (s, 2H), 3.16-3.08 (m, 8H), 3.01-2.81 (m, 4H), 2.76-2.58 (m, 4H), 2.37 (s, 6H), 2.02-1.88 (m, 2H), 1.80-1.72 (m, 8H), 1.71-1.58 (m, 2H), 1.43 (s, 3H), 1.31 (s, 12H), 1.21 (s, 12H), 1.20 (s, 3H).Catalyst 18

[0186] To begin synthesis of catalyst 18, the chemical of Structure 34 was prepared.

[0187] To a pre-cooled (-30°C) stirring mixture of dichlorodimethylsilane (5.12 g, 39.6 mmol) was slowly added solid Li-2-Me-4-Ph-indacenide (2.0 g, 7.93 mmol). The mixture was allowed to warm up and was stirred at room temperature over the weekend. After 3 days solvent was removed in vacuo and the residue was extracted with pentane (3 x 15 mL) and filtered over celite. Solvent removal afforded product as a viscous yellow oil which contained -0.33 equivalent of residual pentane resulting in essentially quantitative yield.

[0188] The *HNMR spectrum of Structure 35 was (400 MHz, Benzene-d6) 67.41 (m, 2H), 7.35 (s, 1H), 7.28 (m, 2H), 7.19 (m, 1H), 6.61 (m, 1H), 3.37 (s, 1H), 2.89 (m, 2H), 2.81 (m, 2H), 2.04 (s, 3H), 1.83 (m, 2H), 0.25 (s, 3H), 0.03 (s, 3H).

[0189] Next the chemical of Structure 35 was prepared.Structure 35

[0190] To a stirring mixture of chloro-dimethyl-(2-methyl-4-phenyl-l,5,6,7-tetrahydro-s-indacen-l-yl) silane (2.9 g, 8 mmol) was added silver tritiate (2.06 g, 8 mmol) at -30°C. The reaction mixture was stirred for 30 minutes. After 30 minutes, the mixture was filtered over celite and concentrated in vacuo to afford the product as viscous amber oil in 98% yield. The oil contained -0.25 equivalent of methylene chloride.

[0191] The 'H NMR spectrum of Structure 35 was (400 MHz, Benzene-d6) 67.35 (m, 2H), 7.28 (m, 2H), 7.20 (m, 1H), 6.54 (m, 1H), 3.24 (s, 1H), 2.86 (m, 2H), 2.74 (m, 2H), 1.89 (s, 3H), 1.81 (m, 2H), 0.21 (s, 3H), -0.12 (s, 3H).

[0192] Next the chemical of Structure 36 was prepared.Structure 36

[0193] To a stirring mixture of [dimethyl-(2-methyl-4-phenyl-l,5,6,7-tetrahydro-s-indacen- 1 -yl)silyl] tritiate (1.08 g, 2.3 mmol) in di ethyl ether was slowly added lithium(2-Me-4-julolildyl-tetrahydroindacenide) (0.94 g, 2.3 mmol) at -30°C. The reaction mixture was allowed to warm up to room temperature and was stirred overnight. After 18 hours, the reaction mixture wasconcentrated in vacuo. The residue was extracted with pentane (3 x 15 mL) and filtered over celite. Solvent removal afforded white foam which was spectroscopically pure as judged by 'HNMR and indicates presence of expected rac / meso structures. Residual 0.66 equivalent of pentane is also observed in the product.

[0194] The 'HNMR spectrum of Structure 36 was (400 MHz, Benzene-d6) 67.54 (m, 3H), 7.45 (s, 2H), 7.31 (m, 3H), 7.20 (m, 1H), 6.97 (m, 1H), 6.71 (m, 1H), 3.87 (two singlets, 2H), 3.08 (m, 2H), 2.94 (m, 7H), 2.82 (s, 3H), 2.09 - 1.94 (4 singlets, 6H), 1.88 (m, 4H), 1.70 (m, 4H), 1.30 (two singlets, 12H), 0.87 (s, 4H), -0.03 - -0.21 (4 singlets, 6H).

[0195] Next the chemical of Structure 37 was prepared.Structure 37

[0196] To a pre-cooled stirring mixture of dimethylsilyl-(2-Me-4-Ph-tetrahydroindacene)(2- Me-4-julolidyl-tetrahydroindacene) (1.6 g, 2.1 mmol) in diethylether was slowly added nBuLi (1.8 mL of 2.5 M solution). The reaction mixture was stirred for 1 hour. After 1 hour, solvent was removed in vacuo and the residue was triturated with pentane. The mixture was then filtered, and the resulting orange solid was washed with pentane (2 x 20 mL) and dried in vacuo to afford final product which was spectroscopically pure and contained 0.5 equivalent of diethylether. The 'H NMR spectrum of structure 37 was (400 MHz, THF-d8) 6 7.56 (m, 4H), 7.31 (m, 4H), 7.17 (m, 1H), 5.97 (s, 1H), 5.88 (s, 1H), 3.12 (m, 4H), 2.89 (m, 6H), 2.83 (m, 2H), 2.42 (s, 3H), 2.40 (s, 3H), 1.92 (m, 4H), 1.86 (m, 4H), 1.33 (s, 12H), 0.79 (s, 6H).

[0197] Next catalyst 18 having the chemical of Structure 38 was prepared.Structure 38

[0198] Solid ZrC14 (0.48 g, 2.1 mmol) was slurried in 40 mL of di ethylether and cooled in the freezer at -30°C. Once cold, dimethylsilyl-(2-Me-4-Ph-tetrahydroindacenyl)(2-Me-4-tetramethyljulolidyl-tetrahydroindacenyl) dilithiate (1.6 g, 2.1 mmol) was slowly added. The mixture was allowed to stir for 1 hour. After 1 hour, solvent was removed in vacuo to afford bright red residue. The residue was extracted with methylene chloride (2 x 20 mL), filtered over celite and concentrated. The residue was then triturated with pentane (15 mL), filtered, and washed with additional pentane (3 x 15 mL). The isolated product was essentially 1: 1 rac / meso mixture. The combined 1.25 g of isolated product was placed in 40 mL of toluene and 6 mL of methylene chloride and heated until dissolved. The mixture was then allowed to cool to room temperature and was placed in a freezer overnight. Fractional crystallization from toluene consistently yielded meso enriched sample in the ratio of -19:1. Between 5 collected fractions 0.325 g of meso enriched material was collected as a bright red powder (18% yield). The remaining supernatant solution was concentrated in vacuo and slurried in 5 mL of pentane. The precipitated solid was collected and dried in vacuo to afford 0.450 g as orange powder which was enriched in -6: 1 ratio towards rac isomer (25% yield).

[0199] The Pseudo-meso enriched compound had a1H NMR spectrum of (400 MHz, Methylene Chloride-d2) 87.49 (m, 6H), 7.36 (m, 1H), 7.25 (m, 3H), 6.59 (s, 1H), 6.50 (s, 1H),3.17 (m, 4H), 2.81 (s, 8H), 2.41 (s, 3H), 2.40 (s, 3H), 1.88 (m, 8H), 1.48 (s, 3H), 1.35 (s, 6H), 1.27 (s, 6H), 1.24 (s, 3H).

[0200] The Pseudo-rac enriched compound had a1H NMR spectrum of (400 MHz, Methylene Chloride-d2) 67.59 (m, 2H), 7.51 (s, 1H), 7.46 (m, 3H), 7.41 (m, 1H), 7.27 (s, 2H), 6.74 (s, 1H), 6.62 (s, 1H), 3.17 (m, 4H), 2.97 (m, 8H), 2.25 (s, 6H), 2.04 (m, 4H), 1.82 (m, 4H), 1.35 (s, 12H), 1.27 (s, 6H).Example 2

[0201] In this example, the julolidine substituted metallocene catalyst compounds prepared in Example 1 were tested for polymerization activity for polypropylene and ethyl ene-propylene co-polymer.

[0202] Polymerization procedure (HT-method): Solution propylene polymerizations were carried out under high-throughput (HT) 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 was introduced 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 1.1-1000 molar equivalents of methylalum oxane (MAO) in toluene was then injected into the reaction vessel along with 500 microliters of toluene. In the case of ethylene propylene copolymerization (EP) the reactors were pressurized with pre-determined amount of ethylene (typically 60 psi). 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 to determine the molecular weight and by DSC to determine melting point.

[0203] Rapid GPC procedure: To determine various molecular weight related values by GPC, high temperature size 5 exclusion chromatography was performed using an automated rapid GPC system. This apparatus was 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 chlorobenzene was 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 and / or Polymer Char IR4 detector. The molecular weights presented are relative to linear polystyrene standards and are uncorrected.

[0204] DSC Procedure-1: For the high throughput samples, the melting temperature (Tm) was 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 was sealed in an aluminum pan and loaded into the instrument at about room temperature. Samples were 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.

[0205] GPC procedure. The samples prepared in lab reactor with supported catalysts were tested using this method. The distribution and the moments of molecular weight (Mw, Mn, Mz, Mw / Mn, etc.), the comonomer content, and the branching index (g') are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5 with a multiple-channel band filter based infrared detector ensemble IR5 with band region covering from about 2,700 cm'1to about 3,000 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 pL flow marker (heptane) added thereto. After loading the vial in the auto-sampler, the oligomer or polymermay 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, Z, using the equation: c=al, where a is the mass constant determined with polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm / mole. The MW at each elution volume is calculated with Equation 1:Equation 1, log( / K) aPS+ 110gM =a + 1+^TT10gM"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 as described in the published in literature (e.g., Sun, T. et al. (2001) Macromolecules, v.34, pg. 6812), except that for purposes of this present disclosure and claims thereto, a = 0.705 and K = 0.0000229 for ethyl ene-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.

[0206] The comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH2 and CH3 channel calibrated with a series of PE and PP homo / copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1,000 total carbons (CH3 / IOOOTC) as a function of molecular weight. The shortchain branch (SCB) content per l,000TC (SCB / 1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH3 / IOOOTC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % comonomeris then obtained from Equation 2 in which f is 9.3, 9.4, 9.6, 9.8, and so on for C3, C4, Ce, Cs, and so on co-monomers, respectively:Equation 2 w2 = f * SCB / 1999TC.

[0207] The bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the entire signals of the CH3 and CH2 channels between the integration limits of the concentration chromatogram. First, the following ratio in Equation 3 is obtained Equation 3 >..T_. Area of C 11; signal within integration limitsBulk IR ratio = -. —,.,.. -: — — —.Area ot CH2 signal within integration limitsThen the same calibration of the CH3 and CH2 signal ratio, as mentioned previously in obtaining the CH3 / 1000TC as a function of molecular weight, is applied to obtain the bulk CH3 / 1000TC. A bulk methyl chain ends per l,000TC (bulk CH3end / 1000TC) is obtained by weight-averaging the chain-end correction over the molecular-weight range. Then Equations 4 and 5 apply Equation 4 w2b = f * bulk CH3 / 1000TCEquation 5 bulk SCB / 1000TC = bulk CH3 / 1000TC - bulk CH3end / 1000TC and bulk SCB / 1000TC is converted to bulk w2 in the same manner as described above.

[0208] The LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions,' Huglin, M. B., Ed.; Academic Press, 1972.), as specified in Equation 6:Equation 6Here, AR(9) is the measured excess Rayleigh scattering intensity at scattering angle 0, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient, P(9) is the form factor for a monodisperse random coil, and Kois the optical constant for the system, as specified in Equation 7:Equation 7where NA is Avogadro’s number, and (dn / dc) is the refractive index increment for the system. The refractive index, n = 1.500 for TCB at 145°C and 1 = 665 nm. For analyzing polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn / dc = 0.1048 ml / mg and A2 = 0.0015; for analyzing ethyl ene-butene copolymers, dn / dc = 0.1048*(l-0.00126*w2) ml / mg and A2 = 0.0015 where w2 is weight percent butene comonomer.

[0209] A high temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, r|s, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [q], at each point in the chromatogram is calculated from the equation [q]= qs / c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as M = KpsMaps+1 / [tj], where apsis 0.67 and Kpsis 0.000175.

[0210] The branching index (g'vis) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, [r|]avg, of the sample is calculated by Equation 8:Equation 8where the summations are over the chromatographic slices, i, between the integration limits.

[0211] The branching index g'visis defined as Equation 9:Equation 9where Mvis the viscosity-average molecular weight based on molecular weights determined by LS analysis and the K and a are for the reference linear polymer, which are, for purposes of this present disclosure and claims thereto, a = 0.705 and K = 0.0000229 for ethyl ene-propylene copolymers and ethylene-propylene-diene terpolymers, a = 0.695 and K = 0.000579 for linearethylene polymers, a = 0.705 and K = 0.0002288 for linear propylene polymers, 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. Calculation of the w2b values is as discussed above.

[0212] DSC Procedure-2. The samples prepared in lab reactor were tested according to DSC Procedure-2. Thermal properties of the polymers were assayed by differential scanning calorimetry (DSC). In brief, peak melting point (Tm), and peak crystallization temperature, (Tc) were determined by the following DSC procedure using a TA Instruments model DSC2500 device. Samples weighing approximately 5 to 10 mg were sealed in an aluminum hermetic sample pan and loaded into the instrument at about room temperature. The DSC data were recorded by first gradually heating the sample to about 200°C at a rate of about 10°C / minute. The sample was kept at about 200°C for 5 minutes, cooled to about -20°C at a rate of about 10°C / minute, followed by an isothermal hold for about 5 minutes, heating to about 200°C at about 10°C / minute, followed by an isothermal hold for about 5 minutes, and finally cooling to about 25°C at a rate of about 10°C / minute. Both the first and second cycle thermal events were recorded. The Tm and Tc values reported in the tables below were obtained during the second heating / cooling cycle unless otherwise noted.

[0213] The results of the polymerization and subsequent testing are shown in Table 1 and Table 2. Table 1 includes propylene polymerization (PP) data for comparative catalysts Ci-Ce and the julolidine substituted metallocene catalyst compounds 11-17. Polymerization was carried out at 70°C in isohexane using 1 mL of propylene. Catalyst amount used was 30 nmol. Table 2 includes ethyl ene-propylene (EP) copolymerization data for comparative catalysts Ci-Cio and julolidine substituted metallocene catalyst compounds 11-18. Polymerizations were carried out at 70°C in isohexane using 1 mL of propylene and 60 psi partial pressure of ethylene. Catalyst amount used was 20 nmol. FIG. 5 is a bar graph comparing polypropylene activity in kg / mmol*h for each of the catalysts. FIG. 6 is a bar graph comparing ethylene-polypropylene copolymer activity in kg / mmol*h for each of the catalysts.Table 1Table 2Based on results described in Tables 1 and 2, julolidine substituted catalysts 11-18 demonstrate significant improvements to catalyst activities relative to the structural counterparts Ci-Cio. Unexpectedly, racemo isomers of catalysts 17 and 18 also provide significant improvements to molecular weight of EP copolymers relative to comparative racemo compounds C7-C10.Example 3

[0214] In this example, supported catalyst were prepared using the julolidine substituted metallocene catalyst compounds of example 1.

[0215] Preparation of silica supported MAO (SMAO). In a large eelstir, 30.0 g of DM-L403 silica (calcined at 400°C) was placed in approximately 340 mL of toluene. The mixture was then cooled to -20°C for 1 hour. After 1 hour, 40.8 g of MAO solution (30 wt% in toluene) was slowly added via addition funnel over 25 minutes. The funnel was rinsed with 2 x 20 mL of toluene. The reaction mixture was allowed to stir for 30 minutes at -20°C and was then allowed to warm up to room temperature. Once at room temperature, the slurry was heated to 100°C for 3 hours. After 3 hours, the slurry was filtered and the obtained SMAO was washed with toluene (2 x 50 mL) and pentane (2 x 50 mL) and dried in vacuo at 60°C for 1 hour to obtain 42.1 g of free-flowing powder.

[0216] Preparation of supported catalysts. The supported catalysts were prepared by a method including: placing 2 g of SMAO in 10 mL of toluene and placed on a shaker. While shaking, 0.63 mL of 1 M solution of triisobutylaluminum was added. The mixture was allowed to shake for 15 minutes at room temperature. After 15 minutes, approximately 18 - 22 pmol of metallocene was added in ca 2 mL of toluene. The reaction mixture was allowed to shake for 3.5 hours. After 3.5 hours, the slurry was filtered, and the solid was washed with toluene (2 x 5 mL) and hexane (2 x 5 mL) and dried in vacuo. Each catalyst was used in reactor testing as 5 wt.% slurry in mineral oil.

[0217] The supported catalysts were utilized in propylene polymerization in a 2 L reactor.

[0218] A 2 L autoclave equipped with a steam jacket and mechanical stirrer was nitrogen purged and heated to 130°C for at least 1 hour. Upon cooling to room temperature, liquid propylene (600 mL), triisobutylaluminum (1.0 mL of 1 M solution in hexane) and desired amount of hydrogen (typically 1 -30 mmol) were added and allowed to mix for 5 minutes. After 5 minutes, catalyst slurry (typically 12.5 - 25.0 mg of dry catalyst) was flushed in the reactor along with 200 mL of liquid propylene. The contents of the reactor were allowed to mix for 5 minutes (pre-polymerization stage), before reactor temperature was raised to 70°C to start the polymerization. After 30 minutes, the reactor was cooled to room temperature, unreacted propylene was vented, and the polymer was collected and allowed to dry overnight.Table 3As indicated in Table 3, inventive catalyst 12 provided approximately 15 - 40% improved catalyst activities in slurry propylene polymerization when compared against its structural analog catalysts C2-C4. In addition to this, catalyst 12 demonstrated improved hydrogen response as indicated by steeper relationship between hydrogen in reactor and MFR and molecular weight. Such unexpected attribute is desired since it allows for broadening of the scope of polymer products that can be prepared within the process constraints.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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;T is a bridging group;each of X1and X2is a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring;R1, R2, R3, and R4are each independently selected from a hydrogen atom, substituted Ci to Ce hydrocarbyl group, or unsubstituted Ci to Ce hydrocarbyl group and, optionally, wherein any adjacent R1, R2, R3and R4are joined to form a cyclic structure;R5- R21are each independently selected from a hydrogen atom, a substituted Ci to Ce hydrocarbyl group, or unsubstituted Ci to C20 hydrocarbyl group;Y is nitrogen or phosphorus; andJ1and J2are each are each independently selected from a hydrogen atom, substituted Ci to Ce hydrocarbyl group, or unsubstituted Ci to C20 hydrocarbyl group and, optionally, J1and J2are fused to form cyclic or polycyclic structure.

2. The catalyst compound of claim 1 represented by the formula:wherein R22is a substituted or unsubstituted C1-C30 hydrocarbyl or substituted or unsubstituted julolidyl group, R23is a hydrogen atom or a substituted or unsubstituted Ci to C20 hydrocarbyl group, and J1and J2are each are each independently selected from a hydrogen atom or substituted or unsubstituted Ci to C20 hydrocarbyl group and, optionally, J1and J2are fused to form cyclic or polycyclic structure.

3. The catalyst compound of claim 1 or 2, wherein R5is a primary substituted or unsubstituted C1-C12 alkyl group.

4. The catalyst compound of any of claims 1-3, wherein R6and R7are a hydrogen atom.

5. The catalyst compound of any of claims 1-4, 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 selected from hydrogen, halogen, Ci to C20 hydrocarbyl, or a Ci to C20 substituted hydrocarbyl, and optionally wherein two or more R* form a cyclic structure individually selected from aromatic, partially saturated, saturated cyclic, or fused ring system.

6. The catalyst compound of any of claims 1-5, wherein Y is nitrogen and R7- R21are independently selected from hydrogen or a primary substituted or unsubstituted C1-C12 alkyl group.

7. The catalyst compound of claim 6, wherein Y is nitrogen and R6, R7, R8, R9, R14-R21are hydrogen and R10- R13are methyl group.

8. The catalyst compound of any of claims 1-7, wherein 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 l,5,6,7,8,9-hexahydrocyclohepta[f]inden-l-ide.

9. A catalyst system comprising a catalyst compound represented by any of the following formulas:

10. A catalyst system of claim 9 further comprising an activator.

11. The catalyst system of claim 10 where activator comprises at least one of aluminoxane or salts of non-coordinating (NCA) anions.

12. The catalyst system of claim 11, wherein the salts of NCA ions 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 the charge d-; and d is an integer from 1 to 3.

13. The catalyst system of any of claims 11 or 12, wherein the NCA activator 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.

14. The catalyst system of claim 11 where aluminoxane activator is present in ratios of greater than 1: 100 relative to metal.

15. The catalyst system of any of claims 9-14, further comprising a support material.

16. The catalyst system of claim 15, wherein the support material is selected from the group consisting of Al₂O₃, ZrO₂, SiO₂, SiO₂ / Al₂O₃, SiO₂ / TiO₂, silica clay, silicon oxide / clay, and combinations thereof.

17. A method comprising:introducing one or more of a C2 to C20 olefin monomer, and a catalyst system of any one of claims 9-16, 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 an alpha olefin polymer or copolymer.

18. The method of claim 17 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- 1 -pentene, vinylcy cl obutane, 1-heptene, 1-octene, 1-decene, 1,5 -hexadiene, 1,7-octadiene and 1,9-decadiene, norbomene, vinylnorbornene, ethylidine norbornene, and combinations thereof.

19. The method of any of claims 17 or 18, wherein the olefin polymer or copolymer has a Mw value of 1,000 to 1,000,000 g / mol, such as from 5,000 to 500,000 such as from 10,000 to 250,000 as measured by gel permeation chromatography.

20. The method of any of claims 17-19, wherein the alpha olefin polymer or copolymer has a Mw distribution with poly dispersity index less than 10.

21. The method of any one of claims 17 to 20, wherein the alpha olefin monomer comprises propylene.

22. The method of any of claims 17 to 21, wherein the alpha olefin polymer or copolymer has a melting point of greater than 120°C.

23. The method of any of claims 17 to 22, wherein the alpha olefin copolymer comprises a comonomer content of 0.01 - 99.99 wt.%.

Images