Cyclopentadienyl / adamantylphosphinimine zirconium and hafnium complexes

Abstract

This description provides zirconium-hafnium complexes containing 1) a cyclopentadienyl ligand; 2) an adamantyl-phosphinemine ligand; and 3) at least one other ligand. The use of the complex, in combination with an activator, as an olefin polymerization catalyst is demonstrated. The catalysts are effective for the copolymerization of ethylene with an alpha olefin (such as 1-butene, 1-hexene, or 1-octene).

Description

Cyclopentadienyl / adamantylphosphinimine zirconium and hafnium complexes Field of Invention The present description relates to novel zirconium and hafnium complexes having a cyclopentadienyl ligand and an adamantil phosphinimine ligand and olefin polymerization catalyst systems employing these complexes. Background of the Invention Group 4 metal complexes having a cyclopentadienyl ligand and a phosphinimine ligand, and the use of the complexes as olefin polymerization catalysts, are described in U.S. Patent No. 6,063,879 (Stephan et al, a NOVA Chemical Interniotal SA). Summary of the Invention In one embodiment, the present description provides a complex number having the formula (PI)(Cp)ML2, where: I) PI is a phosphinemine ligand defined by the formula: R1' R1— PN R1 where N is a nitrogen atom; P is a phosphorus atom; each R1 is either unsubstituted adamantyl or substituted adamantyl; and R1' is selected from the group consisting of Ref. 337830 unsubstituted adamantyl, substituted adamantyl and hydrocarbyl C ia C 6 II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered carbon ring having a delocalized bond within the ring and bonding to M, whose ring is unsubstituted or may be further substituted; III) each L is an activatable ligand; and IV) M is zirconium or hafnium. In another embodiment, the present description provides a polymerization catalyst system comprising: A) a complex having the formula (PI)(Cp)ML2, where: I) PI is a phosphinemine ligand defined by the formula: r; R1— P=N — R1 where N is a nitrogen atom; P is a phosphorus atom; each R1 is either unsubstituted adamantyl or substituted adamantyl; and R1' is selected from the group consisting of unsubstituted adamantyl, substituted adamantyl, and hydrocarbyl Ci to C6; II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered carbon ring having a delocalized bond within the ring and bonding to M, whose ring is unsubstituted or may be further substituted; III) each L is an activatable ligand; and IV) M is zirconium or hafnium; and B) an activator. In another embodiment, the present description provides a process for the polymerization of olefins comprising contacting one or more ethylene and C3 to C10 alpha olefins with an olefin polymerization catalyst system under polymerization conditions; wherein the olefin polymerization catalyst system comprises: A) a complex having the formula (PI)(Cp)ML2, where: I) PI is a phosphinemine ligand defined by the formula: R1' R1— P=NR1 where N is a nitrogen atom; P is a phosphorus atom; each R1 is either unsubstituted adamantyl or substituted adamantyl; and R1' is selected from the group consisting of unsubstituted adamantyl, substituted adamantyl, and hydrocarbyl C ia C 6; II) Cp is a ligand comprising a carbon ring; the delocalized bond within the ring is not further substituted; cyclopentadienyl type that has a 5-membered ring and is attached to M, whose o may be substituted III) each L is an activatable ligand; and IV) M is zirconium or hafnium; and B) an activator. In one embodiment, the present description provides a complex that has the formula: where each L is an activatable ligand; and where M is zirconium or hafnium. In one embodiment, the present description provides a complex that has the formula: where each L is an activatable liquefying agent; and where M is zirconium or hafnium. In another embodiment, the present description provides a polymerization catalyst system comprising: A) a complex that has the formula: where each L is an activatable ligand; and where M is zirconium or hafnium; and B) an activator. In another embodiment, the present description provides a polymerization catalyst system comprising: A) a complex that has the formula: where each L is an activatable ligand; and where M is zirconium or hafnium; and B) an activator. In another embodiment, the present description provides a process for the polymerization of olefins comprising contacting one or more ethylene and C3 to C10 alpha olefins with an olefin polymerization catalyst system under polymerization conditions; wherein the olefin polymerization catalyst system comprises: A) a complex that has the formula: where each L is an active ligand; and where M is zirconium or hafnium; and B) an activator. In another embodiment, the present description provides a process for the polymerization of olefins comprising contacting one or more ethylene and C3 to C10 alpha olefins with an olefin polymerization catalyst system under polymerization conditions; wherein the olefin polymerization catalyst system comprises: A) a complex that has the formula: ινΐΛ / a / zuzz / ui / where each L is an activatable ligand; and where M is zirconium or hafnium; and B) an activator. In one embodiment of the description, an activator consists of a combination of an aluminoxane and an ionic activator (e.g., trityl borate, [Ph3C][B(CgF5)4]). In one embodiment of the description, an activator consists of a combination of an organoaluminum compound and an ionic activator (e.g., triphyll borate, [Ph3C][B(CgF5)4]). Detailed Description of the Invention As used herein, the term unsubstituted means that the hydrogen radicals are attached to the molecular group referred to in the unsubstituted term. The term substituted means that the group referred to in this term has one or more substituents that have replaced one or more hydrogen radicals at any position within the group. Non-limiting examples of residues include halogen radicals (F, Cl, Br), an alkyl group, an alkylaryl group, an arylalkyl group, an alkoxy group, an aryl group, an aryloxy group, an amido group, a silyl group or a germanyl group, hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, phenyl groups, naphthyl groups, C1 to C10 alkyl groups, C2 to C10 alkenyl groups and combinations thereof. As used herein, the terms hydrocarbyl, hydrocarbyl radical, or hydrocarbyl group refer to linear or branched, aliphatic, olefinic, acetylenic, and aryl (aromatic) radicals comprising hydrogen and carbon that are deficient in one hydrogen. The term cyclic hydrocarbyl group denotes hydrocarbyl groups comprising cyclic moieties and which may have one or more cyclic aromatic rings and / or one or more non-aromatic rings. The term acyclic hydrocarbyl group denotes hydrocarbyl groups that do not have cyclic moieties such as aromatic or non-aromatic ring structures present within them. As used herein, the term heteroatom includes any atom other than carbon and hydrogen that can be bonded to carbon. The term containing heteroatoms or hydrocarbyl group containing heteroatoms means that one or more atoms other than carbon may be present in the hydrocarbyl groups. Some non-limiting examples of non-carbon atoms that may be present in a hydrocarbyl group containing heteroatoms are N, O, S, P, and Si, as well as halides such as Br and metals such as Sn. Some non-limiting examples of hydrocarbyl groups containing heteroatoms include imines, amine moieties, oxide moieties, phosphine fractions, ethers, ketones, heterocycles, oxazolines, thioethers, and the like. As used herein, an alkyl radical or alkyl group includes linear, branched, and cyclic paraffin radicals that are deficient in a hydrogen radical; non-limiting examples include methyl (-CH3) and ethyl (-CH2CH3) radicals. The term alkenyl radical or alkenyl group refers to linear, branched, and cyclic hydrocarbons containing at least one carbon-carbon double bond that is deficient in a hydrogen radical. The term alkynyl radical or alkynyl group refers to linear, branched, and cyclic hydrocarbons containing at least one carbon-carbon triple bond that is deficient in a hydrogen radical. As used here, the term aryl group includes phenyl, naphthyl, pyridyl, and other radicals whose molecules have an aromatic ring structure; non-limiting examples include naphthylene, phenanthrene, and anthracene. An alkylyl group is an alkyl group that has an aryl group attached to it; non-limiting examples include benzyl, phenethyl, and tolylmethyl. An arylalkyl is an aryl group that has one or more alkyl groups attached to it; non-limiting examples include tolyl, xylyl, mesityl, and cumyl. An alkoxy group is an oxy group that has an alkyl group attached to it; and includes, for example, a methoxy group, an ethoxy group, an isopropoxy group, and the like. An aryloxy group is an oxy group that has an aryl group attached to it; and includes, for example, a phenoxy group and the like. Adamantyl phosphinimine ligand The adamantyl ligand phosphinimine is defined as: R1' R1p=NR1 where N is a nitrogen atom; P is a phosphorus atom; each R1 is either unsubstituted or substituted adamantyl and R1' is selected from the group consisting of unsubstituted adamantyl, substituted adamantyl and hydrocarbyl Ci to Cg. For reference, the numbering of an adamantyl carbon atom framework is provided below, whether in a substituted or unsubstituted adamantyl moiety as mentioned in this description: In one embodiment of the description, the term unsubstituted adamantyl, as used herein, has a limited meaning: it is restricted to the well-known hydrocarbon cage structure containing 10 carbon atoms and excludes substituted adamantyl. Therefore, the term unsubstituted adamantyl, as used here, excludes cage structures containing more than 10 carbon atoms and also excludes structures containing atoms other than carbon and hydrogen. Those skilled in the art will appreciate that there are two isomers of unsubstituted adamantyl, namely 1-adamantyl (where the adamantyl moiety is attached from a tertiary carbon atom to the phosphorus atom of the phosphinimine ligand) and 2-adamantyl (where the adamantyl moiety is attached from a secondary carbon atom to the phosphorus atom of the phosphinimine ligand). In one embodiment, each of the unsubstituted adamantyl groups in the phosphinimine ligand is 1-adamantyl. In one embodiment of the description, the term substituted adamantyl, as used herein, means that the adamantyl has one or more substituents attached to its 10-carbon structure. Those skilled in the art will appreciate that there are two isomers of a substituted adamantyl, namely, 1-substituted adamantyl (where the substituted adamantyl moiety is attached from a tertiary carbon atom to the phosphorus atom of the phosphinimine ligand) and 2-substituted adamantyl (where the substituted adamantyl moiety is attached from a secondary carbon atom to the phosphorus atom of the phosphinimine ligand). In one embodiment, each of the substituted adamantyl groups in the phosphinimine ligand is a substituted 1-adamantyl. In one form of the description, a substituted adamantil has one or more hydrocarbyl group substituents. In one form of the description, a substituted adamantil has one or more hydrocarbyl group substituents containing heteroatoms. In one form of the description, a substituted adamantil has one or more halide group substituents. In one form of the description, a substituted adamantil has one or more alkyl group substituents. In one form of the description, a substituted adamantil has one or more aryl group substituents. In one form of the description, a substituted adamantil has one or more methyl group substituents. In one form of the description, a substituted 1-adamantyl has one or more hydrocarbyl group substituents. In one form of the description, a substituted 1-adamantyl has one or more hydrocarbyl group substituents containing heteroatoms. In one form of the description, a substituted 1-adamantyl has one or more halide group substituents. In one form of the description, a substituted 1-adamantyl has one or more alkyl group substituents. In one form of the description, a substituted 1-adamantyl has one or more aryl group substituents. In one form of the description, a substituted 1-adamantyl has one or more methyl group substituents. In one embodiment of the description, a substituted 1-adamantyl has a substituent methyl group at position 3 and at position 5. In one embodiment of the description, a substituted 1-adamantyl has a substituent methyl group at position 3, position 5, and position 7. In one form, each R1 is an unsubstituted adamantyl. In one mode each R1 is a substituted adamantil. In one modality, each R1 is an unsubstituted 1-adamantile. In one mode, each R1 is a substituted 1-adamantile. In one embodiment, each R1 is a substituted 1-adamantyl having a substituent methyl group at position 3 and position 5. In one embodiment, each R1 is a substituted 1-adamantyl having a substituent methyl group at position 3, position 5, and position 7. In one modality, R1' is an unsubstituted adamantyl. In one modality, R1' is a substituted adamantite. In one modality, R1' is an unsubstituted 1-adamantile. In one modality, R1' is a substituted 1-adamantile. In one embodiment, R1' is a substituted 1-adamantyl having a methyl group substituent at the 3 and 5 positions. In one embodiment, R1' is a substituted 1-adamantyl having a methyl group substituent at position 3, position 5, and position 7. In one embodiment, R1' is a Ci to Cg hydrocarbyl. Cyclopentadienyl type ligand Cyclopentadienyl-type ligands comprise a five-carbon ring with a delocalized bond within the ring that is attached to the metal, whose ring is either unsubstituted or may be substituted (sometimes referred to simply as Cp ligands). Cyclopentadienyl-type ligands include unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl, and substituted fluorenyl. Hydrogenated versions of indenyl and fluorenyl ligands are also contemplated for use in the current description, provided that the five-carbon ring attached to the metal via the eta-5 (or in some cases eta-3) bond remains intact.An illustrative list of substituents for a cyclopentadienyl-type ligand includes the group consisting of Ci-io hydrocarbyl radicals (the hydrocarbyl radical may be unsubstituted or further substituted, for example, by a halide and / or a hydrocarbyl group; for example, a suitable substituted Ci-io hydrocarbyl radical is a pentafluorobenzyl group such as CH2C6F5); a C1-4 alkyl radical; a Ci-s alkoxy radical; a Cg-ioZ aryl or aryloxy radical; an amide radical that is unsubstituted or substituted with up to two Ci-8 alkyl radicals; a phosphide radical that is unsubstituted or substituted with up to two Ci-g alkyl radicals; silyl radicals of formula -Si(R)3 wherein each R is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, and Cg-io aryl or aryloxy radicals; siloxy radicals and germanyl radicals of formula Ge-(R)3 where R is as directly defined above.Cyclopentadienyl-type ligands may also contain heterocyclic residues or hydrocarbyl groups containing heteroatoms. In one form of the description, the cyclopentadienyl-type ligand is pentamethylcyclopentadienyl. In one form of the description, the cyclopentadienyl ligand is penta(n-propyl)cyclopentadienyl. In one form of the description, the cyclopentadienyl-type ligand is cyclopentadienyl. In one embodiment, the cyclopentadienyl ligand is tetramethyl(pentafluorobenzyl)cyclopentadienyl, CpMe4 (CH2C6F5). In one embodiment, the cyclopentadienyl-type ligand is (pentafluorobenzyl)cyclopentadienyl, Cp(CH2C6F5). In one embodiment, the cyclopentadienyl ligand is tetramethyl(3,5-tert-butylphenyl)cyclopentadienyl, CpMe4(-3,5t-B2-C6H3). In one embodiment of the description, the cyclopentadienyl-type ligand is 1,2,3-trimethyl-4-phenyl-4-hydrocyclopent[b]indolyl. Activable ligand The term activatable ligand refers to a ligand that can be activated by a cocatalyst (also called an activator) to facilitate the polymerization of olefins. An activatable ligand L can be cleaved from the metal center M of the catalyst via a protonolysis reaction or abstracted from the metal center M by activating compounds of suitable electrophilic catalysts or acids (also known as cocatalyst compounds), respectively, examples of which are described below. The activatable ligand L can also be transformed into another ligand that cleaves or extracts from the metal center M (e.g., a halide can be converted into an alkyl group). Without intending to limit itself to any single theory, protonolysis or abstraction reactions generate an active cationic metal center that can polymerize olefins.In embodiments of the present description, the activatable ligand L is independently selected from the group consisting of a hydrogen atom; a halogen atom; a hydrocarbyl radical Ci-io; an alkoxy radical Ci-io; an aryl oxide radical Cs-iol, each of which the hydrocarbyl, alkoxy, and aryl oxide radicals may be substituted or unsubstituted by a halogen atom, an alkyl radical Ci-8, an alkoxy radical Ci-8, an aryl radical Ce-io, or an aryloxy radical; an amide radical that is either unsubstituted or substituted with up to two alkyl radicals Ci-s; and a phosphide radical that is either unsubstituted or substituted with up to two alkyl radicals Ci-g. Two activatable ligands L may also be joined together to form, for example, a substituted or unsubstituted diene ligand (e.g., 1,3-diene). or a group containing delocalized heteroatoms such as an acetate group. The number of activatable ligands depends on the valency of the metal and the valency of the activatable ligand. In some embodiments, preferred phosphinimine catalysts are based on group 4 metals in their highest oxidation state (i.e., 4+). Particularly suitable activatable ligands are monoanionic, such as a halide (e.g., chloride) or a hydrocarbyl (e.g., methyl, benzyl). In some cases, the phosphinemine catalyst metal may not be in its highest oxidation state. For example, a hafnium(III) or zirconium(III) component would contain only one activatable ligand. In one version of the description, the activatable ligand L is methyl. In one version of the description, the activatable ligand L is benzyl (Bn for short). In one version of the description, the activatable ligand L is chloride. The Activator In the present description, the complex is used in combination with at least one activator (or cocatalyst) to form an active polymerization catalyst system for the polymerization of olefins. The activators (i.e., cocatalysts) include ionic activator cocatalysts and aluminoxane cocatalysts and, in some embodiments, may include organoaluminum compounds as cocatalysts. In one embodiment, the activator comprises one or more of the following: an aluminoxane compound, an ionic activator, or an organoaluminum compound. A hindered phenol may optionally be used in combination with an aluminoxane compound or an organoaluminum compound. In one embodiment of the description, the activator is an organoaluminum compound and an ionic activator. In another embodiment of the description, the activator is an aluminoxane compound and an ionic activator. In one embodiment of the invention, the activator is an ionic activator. In one embodiment of the description, the activator is selected from the group consisting of an aluminoxane, an organoaluminum compound, an ionic activator, and mixtures thereof. Aluminoxane (also known as alkylaluminoxane) The activator used to activate the single-site catalyst can be any suitable activator that includes one or more activators selected from the group consisting of alkylaluminoxanes and ionic activators, optionally along with an alkylating agent. Without intending to impose any theory, alkylaluminoxanes are aluminum complex compounds of the formula R42A11O (R4A11O)mAl1R42, where each R4 is independently selected from the group consisting of C1-20 hydrocarbyl radicals and m is from 3 to 50. Optionally, a spherically hindered phenol can be added to the alkylaluminoxane to provide an Al1:hindered phenol molar ratio of 2:1 to 5:1 when the hindered phenol is present. In one form of the description, R3 of alkylaluminoxane is a methyl radical and m is from 10 to 40. Alkylluminoxanes are typically used in a substantial molar excess compared to the amount of group 4 transition metal in the single-site catalyst. Molar ratios of AVz to group 4 transition metal can range from 5:1 to 10,000:1, such as approximately 30:1 to 500:1. It is well known in the field that alkylaluminoxane can perform dual functions as an alkylating agent and an activator. Therefore, an alkylaluminoxane activator is often used in combination with activatable ligands such as halogens. Alternatively, the activator described herein may be a combination of an alkylating agent (which may also serve as a scrubber) with an activator capable of ionizing the group 4 metal of the single-site catalyst (i.e., an ionic activator). In this context, the activator may be selected from one or more alkylaluminoxanes and / or an ionic activator. When present, the alkylating agent can be selected from the group consisting of (R*)pMgX22-P where X2 is a halide and each R* is independently selected from the group consisting of C1-10 alkyl radicals and p is 1 or 2; R*Li where R* is as previously defined, (R*)qZnX22-q where R* is as previously defined, X2 is a halogen and q is 1 or 2; (R4) sA12X23-s where R* is as previously defined, X2 is a halogen and s is an integer from 1 to 3. In some embodiments, R* is a C1-4 alkyl radical and X2 is chlorine. Commercially available compounds include triethylaluminum (TEAL), diethylaluminum chloride (DEAC), dibutylmagnesium ((Bu)2Mg) and butylethylmagnesium (BuEtMg or BuMgEt). Organoaluminum compound In one embodiment, organoaluminum compounds are defined by the formula: Al (R3) m (OR3) n (X)pen where R3 and R3 are each independently hydrocarbyl groups Ci to C20; X is a halide; meter + n + p = 3; ymh 1. In one version of the description, the organoaluminum compound used is defined by the formula: A1R4X(OR5) and where x is from 1 to 3, x+y=3, R4 is a hydrocarbyl group Ci to Cío and R5 is an alkyl or aryl group. In particular forms, organoaluminum compounds include triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, and diethylaluminum ethoxide. Ionic activator The ionic activator can be selected from the group consisting of: (i) compounds of formula [R5]+[B(R6)4]~ where B is a boron atom, R5 is a cyclic C5-7 aromatic cation or a triphenylmethyl cation, and each R6 is independently selected from the group consisting of phenyl radicals that are either unsubstituted or substituted with 3 to 5 substituents selected from the group consisting of a fluorine atom, a C4-4 alkyl or alkoxy radical that is either unsubstituted or substituted with a fluorine atom; and a silyl radical of formula -Si--(R7)3,· where each R7 is independently selected from the group consisting of a hydrogen atom and a C4-4 alkyl radical;and (ii) compounds of formula [(R8)tZH]+[B(R6)4]“ where B is a boron atom, H is a hydrogen atom, Z is a nitrogen atom or a phosphorus atom, t is 2 or 3 and R8 is selected from the group consisting of Ci-s alkyl radicals, a phenyl radical that is either unsubstituted or substituted with up to three C4_4 alkyl radicals, or an R8 taken together with a nitrogen atom can form an anilinium radical and R6 is as defined above; and (iii) compounds of formula B(R6) 3 where R6 is as defined above.; In some embodiments, in the above compounds, preferably R6 is a pentafluorophenyl radical and R5 is a triphenylmethyl cation, Z is a nitrogen atom and R8 is a C1-4 alkyl radical or an R8 taken together with a nitrogen atom forms an anilinium radical. (for example, PhR82NH+, which is substituted by two R8 radicals such as, for example, two C1-4 alkyl radicals). Examples of compounds capable of ionizing the single-site catalyst include the following compounds: tetra(phenyl)boro di triethylamonium, (phenyl)boro di tripropylammonio, tetra (phenyl)boro di tri (n-butyl)ammonio, tetra(p-tolyl)boro di trimethylammonio, tetra(o-tolyl)boro di trimetilamonio, tetra(pentafluorophenyl)boro di tripropylamonium, tetra(o,p-dimethylphenyl)boro di tripropylammonio, tetra(m,mdimethylphenyl)boro di tributilamonio, tetra(ptrifluoromethylphenyl)boro de tributilamonio, tetra (pentafluorophenyl)boro de tributilamonio, tetra(otolyl)boro de tri(n-butyl)ammonio, tetra(phenyl)boro de N,N-dimethylanilinio, tetra (phenyl)boro de N,N-dietilanilinio, tetra(phenyl)n-butylboro de N,N-dietilanilinio, (phenyl)boro de N,N-2,4,6-pentametilanilinio, tetra(pentafluorophenyl) tetraboro de di-(isopropyl)ammonio, tetra(phenyl)boro de dicyclohexilamonio, tetra(phenyl)boro de triphenylphosphonio, tri(methylphenyl)phosphonio, tetra(phenyl)boro de tri(methylphenyl)phosphonio,ινίΛ / a / zuzz / u 1 ¿ / / / tetrakispentafluorophenyl borate of tropyl, tetrakispentafluorophenyl borate of triphenylmethyl, tetrakispentafluorophenyl borate of benzene (diazonium), phenyltris-pentafluorophenyl borate of tropyl, phenyltrispentafluorophenyl borate of triphenylmethyl, phenyltrispentafluorophenyl borate of benzene(diazonium), tetrakis(2,3,5,6-tetrafluorophenyl)borate of tropyl, tetrakis(2,3,5,6-tetrafluorophenyl)borate of triphenylmethyl, tetrakis(3,4,5-trifluorophenyl)borate of benzene(diazonium), tetrakis(3,4,5-trifluorophenyl)borate of tropyl, tetrakis(3,4,5-trifluorophenyl)borate of benzene(diazonium), tetrakis(1,2,2-trifluoroethenyl)borate of tropylium, tetrakis(1,2,2-trifluoroethenyl)borate of trophenylmethyl, tetrakis(1,2,2-trifluoroethenyl)borate of benzene (diazonium), tetrakis(2,3,4,5-tetrafluorophenyl)borate of tropylium, tetrakis(2,3,4,5-tetrafluorophenyl)borate of triphenylmethyl and tetrakis(2,3,4,5-tetrafluorophenyl)borate of benzene (diazonium)., Commercially available activators that are capable of ionizing the group 4 metal of the single-site catalyst include: N,N-dimethylanilinium tetrakispentafluorophenyl borate ([Me2NHPh][B(C6F5)4]); triphenylmethyl tetrakispentafluorophenyl borate ([PhaC][B(CeF5)4]); and trispentafluorophenyl boron and MAO (methylaluminoxane) and MMAO (modified methylaluminoxane). Ionic activating compounds can be used in amounts that provide a molar ratio of group 4 transition metal to boron of 1:1 to 1:6. Optionally, mixtures of alkylaluminoxanes and ionic activators can be used as activators in the polymerization catalyst. Inhibited phenol Non-limiting examples of hindered phenols that may be employed in some embodiments of the present invention include butylated phenolic antioxidants, butylated hydroxytoluene, 2,6-di-tert-butyl-4-ethylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and octadecyl-3(3', 5'-di-tert-butyl-4'-hydroxyphenyl propionate. Catalytic System The catalyst precursor, the activator, or the entire catalyst composition can be impregnated onto a solid, inert support, in liquid form as a solution, dispersion, or pure liquid, spray-dried, in the form of a prepolymer, or formed in situ during polymerization. In the case of a supported catalyst composition, the catalyst composition can be impregnated or deposited onto the surface of an inert substrate such as silica, clay, carbon black, polyethylene, polycarbonate, porous cross-linked polystyrene, porous cross-linked polypropylene, alumina, thorium, zirconia, or magnesium halide (e.g., magnesium dichloride), such that the catalyst composition is between 0.1 and 90 percent by weight of the total weight of the catalyst composition and support. Polymerization process In general, the catalytic composition can be used for the polymerization of olefins by any suspension, solution, slurry, or gas-phase process, using known equipment and reaction conditions, and is not limited to any specific type of reaction system. Generally, olefin polymerization temperatures range from approximately 0°C to approximately 200°C at atmospheric, sub-atmospheric, or superatmospheric pressures. Suspension or solution polymerization processes can use sub-atmospheric or superatmospheric pressures and temperatures in the range of approximately 40°C to approximately 110°C. A useful liquid-phase polymerization reaction system is described in U.S. Patent No. 3,324,095.Liquid-phase reaction systems generally comprise a reactor vessel into which olefin monomer and catalyst composition are added, and which contains a liquid reaction medium to dissolve or suspend the polyolefin. The liquid reaction medium may consist of the bulk liquid monomer or an inert liquid hydrocarbon that is non-reactive under the polymerization conditions employed. Although such an inert liquid hydrocarbon need not act as a solvent for the catalytic composition or the polymer obtained by the process, it typically serves as a solvent for the monomers used in the polymerization. Suitable inert liquid hydrocarbons for this purpose include isopentane, hexane, cyclohexane, heptane, benzene, toluene, and similar compounds. Reactive contact between the olefin monomer and the catalytic composition must be maintained by stirring or constant agitation.The reaction medium containing the olefin polymer product and unreacted olefin monomer is continuously extracted from the reactor. The olefin polymer product is separated, and the unreacted olefin monomer and liquid reaction medium are recycled back to the reactor. One embodiment of the description is an olefin polymerization process comprising contacting one or more ethylene and C3 to C10 alpha olefins with the olefin polymerization catalyst system described herein under polymerization conditions. One embodiment of the description is an olefin polymerization process comprising contacting one or more ethylene and C3 to C10 alpha olefins with the olefin polymerization catalyst system described herein under solution-phase polymerization conditions. One embodiment of the description is an olefin polymerization process comprising contacting ethylene and one or more olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene with the olefin polymerization catalyst system described herein under polymerization conditions. One embodiment of the description is an olefin polymerization process comprising contacting ethylene and one or more olefins selected from the group consisting of 1-butene, 1-hexene, and 1-octene with the olefin polymerization catalyst system described herein under solution-phase polymerization conditions. Gas-phase polymerization When gas-phase polymerization is employed, pressures can range from 6.89 kPa to 6894.76 kPa (1 to 1000 psi), such as 344.74 to 2757.9 kPa (50 to 400 psi), for example, from 689.48 to 2068.43 kPa (100 to 300 psi), and temperatures range from 30°C to 130°C, for example, from 65°C to 110°C. Stirred-bed or fluidized-bed gas-phase reaction systems are particularly useful. In general, a conventional gas-phase fluidized-bed process is carried out by continuously passing a stream containing one or more olefin monomers through a fluidized-bed reactor under reaction conditions and in the presence of a catalyst composition at a rate sufficient to maintain a bed of solid particles in suspension.A stream containing unreacted monomer is continuously drawn from the reactor, compressed, cooled, optionally fully or partially condensed as described in U.S. Patents Nos. 4,588,790 and 5,462,999, and recycled to the reactor. The product is removed from the reactor, and the refill monomer is added to the recycle stream. As desired for system temperature control, any gas inert to the catalyst and reactant composition may also be present in the gas stream. Polymerization can be carried out in a single reactor or in two or more reactors in series and is performed substantially in the absence of catalyst poisons. Organometallic compounds can be used as chelating agents to increase catalyst activity. Examples of chelating agents are metal alkyls, including aluminum alkyls such as triisobutylaluminum. Conventional adjuvants may be included in the process, provided they do not interfere with the catalytic composition's performance in forming the desired polyolefin. Hydrogen or a metallic or non-metallic hydride (e.g., a silyl hydride) may be used as a chain transfer agent in the process. Hydrogen may be used in quantities up to approximately 10 mol of hydrogen per mole of total monomer feed. The polymers that can be produced according to the description include, but are not limited to, ethylene homopolymers, homopolymers of linear or branched higher alpha-olefins containing from 3 to approximately 20 carbon atoms, and interpolymers of ethylene and such higher alpha-olefins, with densities in the range of approximately 0.86 to approximately 0.96. Suitable higher alpha-olefins include, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-l-pentene, 1-octene, and 3,5,5-trimethyl-l-hexene. Polymers defined according to the description may also be based on or contain conjugated or non-conjugated dienes, such as linear, branched, or cyclic hydrocarbon dienes having from approximately 4 to approximately 20 carbon atoms, for example, from 4 to 12 carbon atoms.In some embodiments, preferred dienes include 1,4-pentadiene, 1,5-hexadiene, 5-vinyl-2-norbornene, 1,7-octadiene, vinylcyclohexene, dicyclopentadiene, butadiene, isobutylene, isoprene, ethylidene norbornene, and the like. Aromatic compounds having vinyl unsaturation, such as styrene and substituted styrenes, and polar vinyl monomers, such as acrylonitrile, maleic acid esters, vinyl acetate, acrylate esters, methacrylate esters, vinylitrialkyl silanes, and the like, can also be polymerized according to the description. Specific olefin polymers that can be manufactured according to the description include, for example, polyethylene, polypropylene, ethylene / propylene rubbers (EPR), ethylene / propylene / diene terpolymers (EPDM), polybutadiene, polyisoprene, and the like. Suspension phase polymerization Detailed descriptions of suspension polymerization processes are widely reported in the patent literature. For example, particulate polymerization, or a suspension process in which the temperature is maintained below the temperature at which the polymer dissolves, is described in U.S. Patent No. 3,248,179. Suspension processes include those employing a loop reactor and those using a single stirred reactor or a plurality of stirred reactors in series, in parallel, or combinations thereof. Non-limiting examples of suspension processes include continuous-circuit or stirred-tank processes. Further examples of suspension processes are described in U.S. Patent No. 4,613,484. Suspension processes are carried out in the presence of a diluent hydrocarbon, such as an alkane (including isoalkanes), an aromatic, or a cycloalkane. The diluent can also be the alpha-olefin comonomer used in copolymerizations. Alkane diluents include propane, butanes (i.e., normal butane and / or isobutane), pentanes, hexanes, heptanes, and octanes. The monomers may be soluble in (or miscible with) the diluent, but the polymer is not (under polymerization conditions). The polymerization temperature can range from approximately 5°C to approximately 200°C. In some embodiments, the polymerization temperature is lower than approximately 120°C, such as from approximately 10°C to approximately 100°C. The reaction temperature is selected to produce a particulate ethylene copolymer. The reaction pressure is influenced by the choice of diluent and the reaction temperature.For example, pressures can range from 15 to 45 atmospheres (approximately 220 to 660 psi or approximately 1500 to 4600 kPa) when isobutane is used as a diluent, up to approximately twice that (i.e., 30 to 90 atmospheres, approximately 440 to 1300 psi, or approximately 3000 to 9100 kPa) when propane is used (see, for example, U.S. Patent No. 5,684,097). The pressure in a slurry process must be maintained high enough to keep at least some of the ethylene monomer in the liquid phase. The reaction typically takes place in a jacketed, closed-circuit reactor that has an internal agitator (e.g., an impeller) and at least one settling stage. The catalyst, monomers, and diluents are fed to the reactor as liquids or slurries. The suspension circulates through the reactor and the jacket is used to control the reactor temperature.Through a series of downcomer valves, the slurry enters a sedimentation stage, and then the pressure is lowered to evaporate the diluent and unreacted monomers and recover the polymer, typically in a cyclone. The diluent and unreacted monomers are recovered and recycled back to the reactor. Solution-phase polymerization Solution processes for the copolymerization of ethylene and an alpha olefin having 3 to 12 carbon atoms are well known in the art. These processes are carried out in the presence of an inert hydrocarbon solvent, typically a C5-12 hydrocarbon that may or may not be substituted by a C1-4 alkyl group, such as pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, and hydrogenated naphtha. An example of a suitable solvent that is commercially available is ISOPAR® E (aliphatic solvent Cg-i2, Exxon Chemical Co.) . In general, a solution polymerization process can use one, two (or more) polymerization reactors. In one embodiment, the polymerization temperature in at least one continuous stirred-tank reactor (CSTR) is approximately 80°C to approximately 280°C (e.g., approximately 120°C to 220°C), and a tubular reactor operates at a slightly higher temperature. Cold feed (i.e., cooled solvent and / or monomer) can be added to the CSTRs. The enthalpy of polymerization heats the reactor. The polymerization solution exiting the reactor can be more than 100°C hotter than the reactor feed temperature. The stirring efficiency in the CSTR can be determined by measuring the reactor temperature at several different points. The largest temperature difference (i.e., between the hottest and coldest temperature measurements) is described as the internal temperature gradient for the polymerization reactor. A well-mixed CSTR has a maximum internal temperature gradient of less than 10°C.An example of an agitator system is described in U.S. Patent Assignment No. 6,024,483. In some embodiments, the preferred pressures are approximately 3447.38 to 55,157.07 kPa (500 psi to 8000 psi). In some embodiments, the preferred reaction process is a medium-pressure process, meaning that the pressure in each reactor is less than approximately 6000 psi (approximately 41,000 kilopascals or kPa), for example, approximately 1500 psi to 3000 psi (approximately 10,000–21,000 kPa). If more than one CSTR is used, catalyst can be added to each CSTR to maintain a high reactor speed. The catalyst used in each CSTR can be the same or different, but it is generally preferable to use the same type of catalyst in each CSTR. In some embodiments, at least 60% by weight of the ethylene fed to the CSTRs is polymerized to polyethylene within the CSTRs. For example, at least 70% by weight of the ethylene fed to the CSTRs may be polymerized to polyethylene within the CSTRs. If a mixed catalyst system is to be used in which one catalyst is a single-site catalyst (e.g., when the catalyst is a complex according to this description) and one catalyst is a ZieglerNatta (Z / N) catalyst, then the single-site catalyst can be employed in the first CSTR and the Z / N catalyst can be employed in the second CSTR. A tubular reactor connected to the discharge of at least one CSTR can also be used. If two CSTRs are used in series, the tubular reactor receives the discharge from the second CSTR. The term tubular reactor is intended to convey its conventional meaning: a simple tube. The tubular reactor described here will have a length-to-diameter (L / D) ratio of at least 10:1. The tubular reactor is not stirred. The tubular reactor can be operated adiabatically. Therefore, as polymerization progresses, the remaining comonomer is increasingly consumed, and the solution temperature rises (both of which improve the efficiency of separating the remaining comonomer from the polymer solution). The temperature rise along the length of the tubular reactor can exceed 3°C (i.e., the discharge temperature of the tubular reactor is at least 3°C ​​higher than the discharge temperature of the CSTR feeding the tubular reactor). Optionally, the tubular reactor may also have feed ports for additional catalyst, cocatalyst, comonomer, and / or telomerization agent (such as hydrogen). However, in some embodiments, it is preferable not to add additional catalyst to the tubular reactor. The total volume of the tubular reactor can be at least 10% by volume of the volume of at least one CSTR, especially from 30% to 200% (for clarity, if the volume of the CSTR is 1000 liters, then the volume of the tubular reactor is at least 100 liters; for example, from 300 to 2,000 liters). ινΐΛ / a / zuzz / ui / Addition of Monomers and Solvent Suitable monomers for copolymerization with ethylene include C3-12 alpha-olefins that are either unsubstituted or substituted with up to two C6-alkyl groups. Non-limiting, illustrative examples of such alpha-olefins are one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene. In some embodiments, octene is preferred. In one embodiment, the monomers are dissolved / dispersed in the solvent before being fed to the first CSTR (or, for gaseous monomers, the monomer can be fed into the reactor to dissolve in the reaction mixture). Before mixing, the solvent and monomers are generally purified to remove potential catalyst poisons, such as water, oxygen, or other polar impurities. Purification of the raw materials follows standard practices in the art; for example, molecular sieves, alumina beds, and oxygen-scavenging catalysts are used for monomer purification. The solvent itself (e.g., methylpentane, cyclohexane, hexane, or toluene) can also be treated similarly. In general, the catalyst components can be premixed in the solvent for the reaction or fed as separate streams to each reactor. In some cases, premixing may be desirable to provide reaction time for the catalyst components before they enter the first CSTR. Such an in-line mixing technique is described in the patent literature (in particular, U.S. Patent No. 5,589,555, issued December 31, 1996, to DuPont Canada Inc.). The residence time in each reactor will depend on the reactor design and capacity. Generally, reactors can be operated under conditions that achieve complete mixing of the reactants. As mentioned earlier, polymerization reactors are arranged in series (i.e., with the solution from at least one CSTR being transferred to the tubular reactor). Examples General Experimental Methods All reactions were performed under purified nitrogen using standard Schlenk techniques or in an inert atmosphere glovebox. All solvents were purified by the system described (Pangborn, AB; Giardello, MA; Grubbs, RH; Rosen RK; Timmers, FJ Organometallics 1996, 15, 1518-1520; D. Bradley, G. Williams and Michelle Lawton, J. Organic Chemistry, 2010, 75, 8351-8354) and then stored on activated molecular sieves in a Kontes flask or in an inert atmosphere glovebox (i.e., pentane, heptane, toluene, tetrahydrofuran, dichloromethane). Chloroform was used as received from Sigma. Aldrich. Anhydrous methanol and ethanol were distilled from sodium. Phosphorus chloride, adamantane, aluminum chloride, lithium aluminum hydride, silver trifluoromethane sulfonate, 1-adamantol, trimethylsilyl trifluoromethane sulfonate, and cyclopentadienyltitanium trichloride were used as received from Sigma Aldrich. Triethylamine was purchased from Sigma Aldrich and distilled over activated molecular sieves prior to use. The deuterated solvents (tetrahydrofuran-dg, toluene-dg) were purchased from Aldrich and stored over activated 4A molecular sieves. The deuterated solvent (acetonad6, bromobenzene-d5, chloroform-d, dichloromethane-d2, tetrahydrofuran-dg, toluene-dg) was purchased from Cambridge Isotope and stored on activated 4 Å molecular sieves. NMR spectra were recorded on a Bruker spectrometer at 400 MHz (pH: 400.1 MHz, 19F: 376 MHz, 31P: 162 MHz). Cp*(tBugPN)Hf(CH2Ph)2 was prepared from Cp*(tBugPN)HfCl2(Can. J. Chem. 2009, 87, 1163-1172) and benzyl magnesium chloride. Molecular weight (Mw, Mn, Mz, g / mol), molecular weight distribution (Mw / Mn), and average molecular weight z (Mz / Mw) distribution were analyzed by gel permeation chromatography (GPC) using a Waters 150c instrument with 1,2,4-trichlorobenzene as the mobile phase at 140°C. Samples were prepared by dissolving the polymer in this solvent and processed without filtration. Molecular weights are expressed as polyethylene equivalents with a relative standard deviation of 2.9% for number-average molecular weight (Mn) and 5.0% for weight-average molecular weight (Mw). Polymer sample solutions (1–2 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating a wheel for 4 hours at 150°C in an oven. The antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture to stabilize the polymer against oxidative degradation.The BHT concentration was 250 ppm. Sample solutions were chromatographically analyzed at 140°C using a PL 220 high-temperature chromatography unit equipped with four SHODEX® columns (HT803, HT804, HT805, and HT806) with TCB as the mobile phase at a flow rate of 1.0 mL / min, and a differential refractive index (DRI) detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect the columns from oxidative degradation. The sample injection volume was 200 mL. Raw data were processed using CIRRUS® GPC software. The columns were calibrated with narrow-distribution polystyrene standards. Polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in ASTM D6474. Comonomer content by Fourier transform infrared spectroscopy (FTIR): The amount (mol% or wt%) of comonomer in an ethylene interpolymer product was determined by FTIR and reported as the short-chain branch (SCB) content with dimensions of CH3# / 1000C (number of methyl branches (or short-chain branches, SCBs) per 1000 carbon atoms). This test was completed in accordance with ASTM D6645-01 (2001), using a compression-molded polymer plate and a Thermo-Nicolet 750 Magna-IR spectrophotometer. The polymer plate was prepared using a compression molding device (Wabash-Genesis series press) in accordance with ASTM D4703-16 (April 2016). Preparation of bis(1-adamantyl)phosphinic chloride At room temperature, phosphorus chloride (100 g; 728 mmol) was added to adamantane (27 g; 198 mmol; 1.06 equiv.) and aluminum chloride (25 g; 187 mmol) using a large stirring rod for effective stirring. The solution was stirred overnight at 90°C. The reaction was cooled, and the excess phosphorus chloride was removed by distillation. Degassed chloroform (60 mL) was added to form a suspension. The suspension was cooled to 0°C, and degassed water (300 mL) was added dropwise with vigorous stirring for 30 minutes. The suspension was filtered, and the filtrate was separated. The organic layer was collected. The aqueous layer was extracted with dichloromethane. The chloroform and dichloromethane solutions were combined and dried over MgSO₄. A white solid (27.0 g, 41%) was obtained after pumping out the volatiles. Preparation of bis(1-adamantyl)phosphine A solution of bis(1-adamantyl)phosphinic chloride (27.0 g, 76 mmol) in THF (200 ml) at At -40°C, lithium aluminum hydride was added (7.25 g, 191 mmol) as a solid in small portions over 1.5 hours in a glove box. The suspension was allowed to warm to room temperature overnight. The solution was filtered to remove the gray solid. The filtrate was pumped to dryness. The product was extracted four times with pentane (4 x 200 ml) and the pentane was evaporated to give a white solid (19.7 g, 86%). 3H NMR (CD2Cl2, δ, ppm): 2.78 (d, Jph = 208 Hz, H), 1.91 (m, 18H), 1.72 (s, 12H). VpH NMR (CD2Cl2, δ, ppm): 17.70 (s). Preparation of 1-adamantylacetate At room temperature, silver trifluoromethane sulfonate (0.040 g, 0.16 mmol; 0.01 equivalents) was added to a mixture of 1-adamantanol (2.35 g; 15.4 mmol; 1.00 equivalents) and acetic anhydride (2.2 mL, 23.3 mmol; 1.50 equivalents). The reaction was stirred at 60°C overnight. The reaction was cooled to room temperature, and a saturated aqueous sodium bicarbonate solution (2.5 mL) was added. The reaction was stirred for 30 minutes and extracted with pentane (3 x 10 mL). The organic layers were combined and dried over MgSO₄. The organic layer was filtered, and the volatiles were removed to give a clear, colorless liquid (0.91 g, 91%). V NMR (CD2C12, δ, ppm): 2.14 (br, 3H), 2.09 (s, 6H), 1.92 (s, 3H), 1.66 (s, 6H). Tri(1-adamantyl)phosphine preparation At room temperature, trimethylsilyl trifluoromethane sulfonate (8.5 mL; 46.5 mmol; 1.20 equiv.) was added to a solution of bis(1-adamantyl)phosphine (11.75 g; 38.9 mmol; 1.00 equiv.) and 1-adamantyl acetate (8.30 g; 46.5 mmol; 1.10 equiv.) in dichloromethane (100 mL). The reaction was stirred at room temperature for 24 hours. Trimethylamine (26 mL; 187 mmol; 4.83 equiv.) was added dropwise, and the reaction was stirred for 30 minutes. Volatiles were removed under vacuum. The residue was suspended in toluene and separated by filtration to obtain a white solid. The solid was suspended in degassed ethanol and filtered. The white solid was washed with ethanol (3 x 50 ml) and dried under vacuum to give pure tri(1-adamantyl)phosphine (15.79 g, 93%). Y NMR (CD2C12, δ, ppm): 2.21 (br, 18H), 1.92 (s, 9H), 1.74 (quartet, 18H). 31P{1H} NMR (CD2Cl2, δ, ppm): 59.23. Preparation of N-trimethylsilyl Tri(ladamantyl)phosphinemine SiMe3 To a solution of tri(1-adamantyl)phosphine (10.0 g; 23.0 mmol) in toluene (250 ml) at room temperature, trimethylsilylazide (3 ml) was added. The solution was heated to 90°C and then 12 ml of trimethylsililazide was added for a total of 12 ml of trimethylsililazide (12 ml, 90.4 mmol, 3.95 equiv.). The reaction was heated under reflux at 110°C for 4 hours. The reaction was cooled to room temperature and the volatiles were removed under vacuum to give a white solid (11.45 g, 95%). 3H NMR (toluene-ds, δ, ppm): 2.31 (br, 18H), 1.92 (s, 9H), 1.74 (quartet, 18H), 0.47 (s, 9H). NMR31P{1H} (toluenods, δ, ppm) : 19.3 (s). Preparation of Tri(1-adamantyl)phosphinemine Methanol (200 mL) was added to a solution of trimethylsilyl tri(1-adamantyl)phosphinimine (7.09 g, 13.5 mmol; 1.00 equiv.) and cesium fluoride (4.26 g, 28.0 mmol; 2.07 equiv.) in THF (200 mL) at room temperature. The reaction was heated to 60°C overnight. The reaction was cooled to room temperature, and the volatiles were removed under vacuum. The white residue was resuspended in dichloromethane (25 mL) and filtered by cannula filtration. The solid was washed four times with dichloromethane (4 x 10 mL). The filtrate was pumped to dryness to yield a white solid (0.99 g, 100%). 7H NMR (CD2C12, δ, ppm): 2.30 (br, 18H), 1.99 (s, 9H), 1.74 (quartet, 18H), -0.26 (s, 1H). NMR ^PpH} (CD2C12, δ, ppm): 45.59. Preparation of lithium tri(1-adamantyl)phosphinimine salt A suspension of tri(1-adamantyl)phosphinemine (1.63 g; 3.61 mmol) in pentane (60 mL) was added dropwise to n-butyllithium (1.6 M in hexanes, 2.60 mL, 1.15 equiv.) for 10 min at room temperature in a glove box. The suspension was stirred overnight and cooled in a freezer at -35°C for 5 hours and filtered. The solid was washed with cold pentane (-35°C, 2 x 30 mL) and vacuum dried (1.53 g). NMR4H (THF-dg, δ, ppm) : 2.34 (br.s,18H), 1.93 (d, 9H), 1.76 (d,9H) 1.70 (s, 6H) . NMR 00} (THF-dg, δ, ppm): 42.15 (s). Preparation of hafnium pentamethylcyclopentadienyltri(1-adamantyl)phosphiniminate dichloride, Cp* (AdgPN)HfClg (Ad = 1-adamantyl; Cp* = pentamethylcyclopentadienyl) nBuLi (1.6, 1.38 mL, 2.21 mL) was added to a suspension of tri(1-adamantyl)phosphinemine (0.994 g, 2.20 mL) in toluene (40 mL) in a glove box. The reaction was stirred at room temperature for 1 hour to produce a suspension of Ad3P=NLi (Ad: 1-adamantyl) in toluene. This Ad3P=NLi suspension was slowly added to a stirred solution of Cp*HfC13 in toluene (~30 mL) at -70°C. The reaction was warmed to room temperature and stirred overnight. The LiCl produced was separated by filtration, and the filtrate was concentrated by vacuum pumping to approximately 10 mL. The product crystallized in approximately 8 hours. Pentane (10 mL) was added dropwise to the supernatant, causing further product crystallization. The mother liquors were decanted, and the solid was washed with a pentane / toluene mixture (50 / 50, 50 mL) and vacuum dried (1.25 g). δ-NMR (toluene-ds, δ, ppm): 2.70–2.30 (very broad s, 18H), 2.26 (s, 15H), 1.95 (broad s, 9H), 1.84–1.67 (very broad s, 6H), 1.615 (double broad, 9H, J = 9Hz). 31P{1H} NMR (toluene-dg, δ, ppm): 29.8 (s). Preparation of hafnium dimethyl pentamethylcyclopentadienyl tri(1-adamantyl)phosphiniminate To a solution of Cp* (1-AdgPN) Hf CI2 (644 mg; 0.77 mmol) in toluene (20 mL) methylmagnesium bromide (0.90 mL; 2.70 mmol; 3.50 equiv.; 3.0 M in diethyl ether) was added at room temperature. The mixture was stirred for 2 hours followed by vacuum removal of the solvent. The residue was ground in toluene (20 mL) and dried under vacuum. Toluene (50 mL) was added, and the suspension mixture was filtered. A fine white solid (594 mg, 97%) was collected by recrystallization of the filtrate. 3H NMR (toluene-dg, δ, ppm): 2.43 (s, wide, 18H), 2.16 (s, 15H), 1.96 (s, wide, 9H), 1.69 (dd, J = 50.2 Hz, 18H), -0.03 (s, 6H). ^PpH} NMR (toluene-d8, δ, ppm): 25.06 (s). Preparation of hafnium dibenzyl pentamethylcyclopentadienyl tri(1-adamantyl)phosphiniminate Benzylmagnesium chloride was added to diethyl ether (1.0 M, 5 mL, 5 mL) to a toluene solution of Cp*(1Ad3PN)HfC12 (1.4 g, 1.68 mL) in toluene (30 mL) at room temperature. The mixture was stirred overnight and pumped to dryness. Toluene (30 mL) was added to the residue to make a suspension, which was filtered to remove the solid. The solid was rinsed with toluene (10 mL). The filtrate was pumped to dryness, and toluene (30 mL) was added to prepare a solution, which was again pumped to dryness. Toluene (30 mL) was added again to the solid to make a solution, which was filtered to remove a very small amount of solid. The filtrate was concentrated to approximately 5 mL and heptane was added. The product crystallized as a white solid at -35°C (0.74 g). 1H NMR (toluene-dg, δ, ppm): 2.43 (s, width, 18H), 2.16 (s, 15H), 1.96 (s, width, 9H), 1.69 (dd, J = 50.2 Hz, 18H), -0.03 (s, 6H). 1H NMR (toluene-dg, δ, ppm): 25.06 (s). Preparation of bis (3,5-dimethyl-l-adamantyl)phosphine, (3,5Me2-1-Ad)2PH) 1,3-Dimethyladamantane (10 g, 60.86 mmol) and A1C13 (9.5 g, 71 mmol) were weighed into a 150 mL Schlenk flask with a large stirring rod. PCI3 (40 mL) was added to the flask. The mixture was stirred and heated to 90°C overnight. An orange suspension was produced. Excess PCI3 was removed by distillation at 115–120°C. The flask was cooled to room temperature, and degassed chloroform (100 mL) was added. The flask was cooled to 0°C, and degassed water (20 mL) was added dropwise under nitrogen from a syringe over approximately 1 hour. An additional 15 mL of water was added to the extinguished reaction. The contents were filtered through a medium glass frit in air and the solid was rinsed with dichloromethane (~50 ml). The orange filtrate was collected, dried with anhydrous magnesium chloride and filtered. The dried filtrate was pumped to dryness to give crystalline (3,5-Me2~l-Ad) 2P (0) C1 (15.77 g) which was used as is in the following reaction. The product of the last reaction was dissolved in THE (150 mL). The solution was cooled to -10°C in a glovebox. 3.5 g of LÍAIH4 (excess) was added to THF (~50 mL) from a dropping funnel over approximately 1 hour. The reaction was stirred overnight. The following morning, the temperature was raised to 40°C for 2 hours. The solvent was pumped off. The residue was extracted with pentane (3 x 100 mL), and the pentane solution was pumped to dryness to give the product, 3,5-Me2~l-Ad) 2PH, as a crystalline solid (8.0 g). NMR 1.32-1.15 (m, 8H), 1.01 (s, 4H), 0.78 (s, 12H). NMR31P (toluene-d8, d, ppm): 14.70 (s). Preparation of (1-adamantyl) bis (3,5-dimethyl-adamantyl)phosphine, (1-Ad) (3, 5-Me2l-Ad)2P Bis(3,5-dimethyl-l-adamantyl)phosphine (13.95 mmol) and 1-adamantylacetate (2.87 g, 14.78 mmol) were weighed into a 250 mL round-bottom flask, to which 50 mL of dichloromethane was added. Trimethylsilyl trifluoromethanesulfonate (3.38 g, 15.20 mmol) was added. The solution was stirred for 24 hours, and triethylamine (7.05 g, 70 mmol) was added. The solution was stirred for 0.5 hours and pumped to dryness. The solid was extracted with degassed ethanol at 65°C (3 x 100 mL) and filtered. The solid (which was insoluble in EtOH) was dried under vacuum (3.50 g, 51% yield). 3H NMR (toluene-da, d, ppm): 2.37 (br.s, 8H), 2.17 (br.s, 6H), 1.97 (dd, J = 33 Hz, J = 15 Hz, 15H), 1.73 (dd, J = 45, J = 12 Hz, 7H), 1.32 (dd, J = 35 Hz, J = 12 Hz, 7H), 1.075 (dd, J = 30, J = 10, 10H), 0.847 (s, 12H). NMR31P (toluene-da, d, ppm): 55.9 (s). Preparation of (1-adamantyl)bis(3,5-dimethyl-154adamantyl) (N-trimethylsilyl)phosphinamine,(1-Ad)(3,5-Me2~l~ Ad)2) P=NSiMe3 (1-Adamantyl)bis(3,5-Me2-l-adamantyl)2phosphine (3.50 g, 7.10 mmol) was weighed into a 250 ml Schlenk flask. Toluene (~70 ml) and trimethylsilyl azide (3.0 ml, 21.3 mmol) were added. The mixture was heated to 110°C for 6 hours and the contents were pumped to dryness to give a foam that solidified to give a white solid (quantitative yield). 3H NMR (toluene-d3, d, ppm): 2.361 (br.s, 8H), 2.159 (br.s, 5H), 2.08-1.89 (m, 14H), 1.69 (dd, J = 44 Hz, J = 12Hz, 8H), 1.29 (dd, J = 51 Hz, J = 12 Hz, 11H), 1.065 (dd, J = 33 Hz, J = 13 Hz, 6H), 0.854 (s, 12H), 0.450 (s, 9H). NMR31P (toluene-dg, d, ppm): 18.7 (s). Preparation of (1-adamantyl) bis (3,5-dimethyl-adamantyl) phosphinimine, (1-Ad) (3,5-Me2l-Ad) 2) P=NH (1-Adamantyl)bis(3,5-dimethyl-l-adamantyl)(N-trimethylsilyl)phosphinimine (1-Ad'2) (1-Ad)P=NSiMe3 (0.985 g, 1.70 mmol) was weighed into a 100 mL Schlenk flask. THF (40 mL) was added. Dry CsF (0.90 g, 5.9 mmol) was weighed into a 50 mL Hypo vial to which 35 mL of degassed absolute MeOH was added to dissolve the CsF. The methanol solution was transferred to the Schlenk flask and the mixture was stirred at 60°C under 20.68 kPa (3 psi) of nitrogen for 6 hours. The solution was pumped to dryness and the residue was extracted with 80 mL of pentane. The pentane solution was filtered and the filtrate was pumped to dryness to give 0.80 g of pure product. 1H NMR (toluene-d8, d, ppm): 2.41 (br.s, 6H), 2.21 (br.s, 4H), 2.08-1.96 (m, 10H), 1.91 (br.s, 3H), 1.68 (dd, J = 42 Hz, J = 13 Hz, 6H), 1.273 (dd, J = 57 Hz, J = 13 Hz, 9H), 1.04 (dd, J = 30 Hz, J = 13 Hz, 4H), 0.836 (s, 12H), -0.45 (v.br.s, 1H). NMR31P (toluene-dg, d, ppm): 41.6 (s). Preparation of (pentamethylcyclopentadienyl) (1adamantyl)bis(3,5-dimethyl-l-adamantyl)phosphiniminate zirconium dichloride, Cp*[(1-Ad) (3, 5-Me2-l-Ad)2PN]ZrCl2ινΐΛ / a / zuzz / ui / [(l-AdY)(l-Ad)P=NH (1.085 g, 2.13 mmol) (1-Ad' is 3,5-dimethyl-l-adamantyl)] was weighed into a 100 mL hypo vial and toluene (40 mL) was added. nBuLi in hexanes (1.6 M, 1.45 mL) was added dropwise to the stirred suspension. In approximately 10 minutes, the suspension became a clear solution, which was stirred overnight. Pentamethylcyclopentadienylzirconium trichloride (0.709 g, 2.13 mmol) was weighed into a 100 mL Schlenk flask, and toluene (25 mL) was added. The solution was stirred for approximately 10 minutes and cooled to -78°C for 0.5 hours. The solution from the hypo vial containing [(1-AdY)(1Ad)P=NLi] was transferred dropwise to the Schlenk flask through a 20-gauge cannula for 10 minutes. The vial was rinsed with toluene (2 x 4 mL), and the toluene washes were added to the Schlenk flask. After stirring the reaction at 78°C for approximately 10 minutes, the cold bath was removed, and the reaction was stirred at room temperature for 24 hours. No precipitate was observed. At approximately 28 hours, the solution began to cloud. The reaction was stirred for another 3 hours and the solution was filtered through Celite to remove the LiCl. The filtrate was pumped to remove the toluene, and a thick oil was obtained.Pentane (approximately 5 ml) was added until the solution became cloudy. The solution was placed in a freezer at -35°C overnight and the product solidified. The mother liquors were pipetted and the solid was washed with pentane to give 1.39 g of white solid. 1H NMR (toluene-dg, d, ppm): 2.8-2.3 (br.s, 8H), 2.24 (s, 15H), 2.20 (s, 1H), 2.12 (s, 2H), 2.02 (br.s, 5H), 1.94 (br.s, 4H), 1.87-1.66 (br. m, 3H), 1.65-1.55 (br. s, 4H), 1.43-1.30 (br.s, 3H), 1.30-1.15 (br. m, 7H), 1.07-0.98 (m, 3H), 0.897 (br. s, 12H). NMR31P (toluene-dg, d, ppm): 25.6 (s). Preparation of zirconium dibenzyl (pentamethylcyclopentadienyl) (1adamantyl)bis(3,5-dimethyl-l-adamantyl)phosphiniminate, Cp*[(l-Ad) (3,5-Me2~l~Ad)2PN]Zr(CHgPh)2 A solution of Cp*[(l-Ad)(1-Ad'2)PN]ZrCl2 (1.29 g, 1.604 mmol) in toluene (30 mL) was cooled in a freezer at -35°C for 0.5 hours. PhCH2MgCl in Et2O (1 M, 3.7 mL) was added to the solution. The mixture was stirred overnight and filtered. The filtrate was pumped to dryness, and toluene (10 mL) was added to dissolve the solid. A small amount of solid was filtered off, and the filtrate was pumped to dryness again. Pentane (~10 mL) was added to dissolve the solid. The cloudy pentane solution was filtered to remove the solid, and the clear filtrate was pumped to approximately 5 mL. The product did not crystallize at -35°C. The solution was pumped to ensure that all the toluene was removed. The solid (1.20 g) was very soluble in pentane. 3H NMR (toluene-da, d, ppm): 7.21-6.82 (m, 10H), 2.57-2.32 (br. s, 8H), 2.29-2.17 (m, 7H), 2.16-2.13 (br.m, 3H), 2.12 (s, 2H), 2.06-2.01 (br.s, 5H), 1.97 (s, 15H), 1.95-1.90 (br.s, 3H), 1.84-1.55 (br.m, 7H), 1.48-1.14 (br.m, 12H), 1.06-0.99 (m, 3H), 0.94-0.84 (br.s,. 12H). RMN31P (toluene-dg, d, ppm) : 21.3 (s) . Preparation of dichloride of (pentamethylcyclopentadienyl)(1-adamantyl)bis(3,5-dimethyl-ladamantyl) phosphiniminate hafnium,Cp* [(1-Ad) (3,5-Me2~lAd)2PN]HfCl2 nBuLi (1.6 M, 1.35 mL, 2.16 mmol) was added to a toluene solution (30 mL) of (1-Ad)(1-Ad'2)P=NH (1.00 g, 1.97 mmol) at room temperature. The solid dissolved very rapidly after the addition. The solution was stirred for 2 hours and added to a suspension of Cp*HfCl3 (0.838 g, 1.97 mmol) in toluene (40 mL) at -70°C. The resulting clear solution was allowed to warm to room temperature and stirred over a weekend. The cloudy solution was filtered to remove the fine solid, and the filtrate was pumped to dryness. The residue was thoroughly extracted with pentane (3 x 10 mL). A small amount of pentane-insoluble solid was found to be the ligand (1-Ad)(1-Ad'2)P=NH. The pentane solution was pumped to dryness. RMN3H (tolueno-dg, d, ppm): 2.7-2.3 (v.br.s, 8H), 2.26 (s, 15H), 2.03 (br.s, 5H), 1.94 (br.s, 5H), 1.63-1.69 (v.br., 3H), 1.61 (br.d., 4H), 1.43-1.13 (br.m, 13H), 1.02 (br.d., 3H), 0.90 (multiple s, 12H). RMN31P (tolueno-dg, d, ppm): 29.2 (s). Preparation of dibencil(pentametilciclopentadienil) (1adamantil)bis(3,5-dimetil-l-adamantil)fosfiniminato from hafnio, Cp*[ (1-Ad) (3,5-Me2-l-Ad)2PN]Hf(CH2Ph)2 The solid from the previous reaction was dissolved in toluene (35 mL). PhCH₂MgCl₂ (1.0 M in diethyl ether, 7 mL) was added. The mixture was stirred overnight and pumped to dryness. The foamy solid was extracted with pentane (150 mL). The pentane solution was filtered, and the volume was reduced to approximately 50 mL by vacuum pumping. The cloudy solution was filtered, and the clear filtrate was pumped to dryness. The solid was redissolved in pentane. A small amount of solid did not dissolve and was filtered out. The filtrate was pumped to dryness to give 1.47 g of product. RMNXH (toluene-dg, d, ppm): 7.24–7.10 (m, 7H). 6.92-6.84 (m, 2H), 6.80-6.70 (m, 1H), 2.60-2.32 (br.s, 6H), 2.23 (m, 5H), 2.06-2.01 (br.s, 4H), 1.99 (s, 15H), 1.96-1.89 (br.m, 4H), 1.78-1.67 (br.m, 5H), 1.66-1.57 (br.m, 4H), 1.441.26 (br.m, 9H), 1.26-1.16 (br.d, 5H), 1.07-1.0 (br.d, 3H), 0.89 (slightly br.s, 12H). NMR31P (toluene-dg, d, ppm): 26.2 (s). Preparation of dibencil(pentamethylcyclopentadienyl) (tri (1adamantyl)fosphiniminate) zirconium, Cp* (1-AdgPN) ZrBn2ινΐΛ / a / zuzz / ui / A toluene solution of Cp*Zr(ClPh)3 in a 20 mL hypovial was added to a suspension of l-Ad3P=NH in toluene (~15 mL) in a 100 mL Schlenk flask at -70°C. The hypovial was rinsed with toluene (2 x 3 mL) and the rinse solution was added to the Schlenk flask. The reaction mixture was allowed to warm to room temperature with the bath cold and stirred overnight. The solution was pumped to dryness. 3H NMR showed a small amount of Cp*Zr(ClPh)3 in addition to the product (from the peak of the Cp* methyl signal). 3P NMR showed a singlet (product) and very small amounts of impurities. The solid was redissolved in toluene and the solution volume was reduced to approximately 5 mL by vacuum pumping. Pentane (5 ml) was added dropwise to the toluene solution, which was then placed in a freezer at -35°C. The product did not crystallize. More pentane (approximately 5 ml) was added to the solution, and the solution was returned to the freezer overnight.Crystallized product. The mother liquor was separated. The solid was washed with pentane (2 x 5 ml) and vacuum dried (0.45 g). RMNXH (toluene-ds, d, ppm): 7.19-7.11 (m, 8H), 6.87-6.81 (m, 2H), 2.38-2.23 (m, 22H), 1.99 (s, 15H), 1.94 (br.s, 10H), 1.81-1.67 (br. m, 9H), 1.66-1.59 (br.d, 10H). RMN31P (toluene-de, d, ppm): 22.3 (s). Preparation of 2,3,4,5-tetramethyl[1-(3,5-di-tert-butyl)]cyclopentadiene, 3,S-tEYPh-MeYpH l-Bromo-3,5-di-tert-butylbenzene (2.69 g, 10 mmol) was added in small portions to 350 mg of activated magnesium flakes (14.6 mmol) in 3 mL of THF. The reaction began in approximately 5 minutes when the solution turned brown. Approximately 15 mL of THF was added to the reaction flask, and the remaining l-bromo-3,5-di-tert-butylbenzene was gradually added in THF. The reaction temperature was maintained at 50°C, and the mixture was stirred for 6 hours to produce the Grignard reagent. The solution was filtered to remove unreacted magnesium (which was eliminated as a pyrophoric solid), and the filtrate was added to a solution of 1,2,3,4-tert-methylcyclopenten-l-one in 30 mL of THF. After stirring at room temperature for 1 hour, the reaction solution was heated to 70°C overnight. The solution was then cooled to room temperature and added to a stirred aqueous solution of HCl (15 mL).After one hour, the product was prepared by diethyl ether extraction to provide 2.8 g of the 3,5-di-t-butylphenyl-tetramethylcycloentadiene isomers. Preparation of 2,3,4,5-tetramethyl[1-(3,5-di-tert-butylphenyl)]cyclopentadienyl hafnium trichloride, (2,3,4,5Me4) (3,5~tBu2Ph) CpHfCI3 3,5-Di-t-Butylphenyl-tetramethylcycloentadiene (3.50 g, 10.8 mmol) was weighed into a 100 mL round-bottom flask in a glove box. Diethyl ether (50 mL) was added. Benzyl potassium (1.406 g, 10.8 mmol) was added in small portions to the solution. An immediate precipitate was observed. After stirring the reaction for 1.5 hours, the suspension was filtered to remove any diethyl ether-soluble byproducts. The solid was rinsed with diethyl ether (2 x 5 mL) and pentane (10 mL) and dried under vacuum. The solid was dissolved in THE (30 mL) and MesSiCl (2.0 g, 18.4 mmol) was added. The solution was stirred overnight and pumped to dryness. Note: KCl dissolved in the product. Pentane (30 ml) was added to the liquid, a lot of precipitate (KC1) was observed, which was filtered out and the pentane filtrate was pumped to dryness to give a viscous oil of 3,5-tBu2Ph-Me4Cp-SiMe3. The product of the previous reaction (1.015 g, 2.652 mmol) was dissolved with heptane (~20 mL). The solution was added to a 100 mL round-bottom flask containing HfC14 (0.860 ± 2.68 mmol). The suspension was heated to 70°C overnight. The white suspension changed to a nearly homogeneous, opaque red solution. Heptane was removed by vacuum pumping, and the solid was extracted with pentane (30 mL). The pentane solution was filtered to remove a small amount of solid, and the filtrate was reduced to approximately 3 mL. The product crystallized at -35°C overnight (1.173 g). NMR (toluene-dg, d, ppm): 7.50 (s, 1H), 7.32 (s, 2H), 2.25 (s, 6H), 2.00 (s, 6H), 1.32 (s, 18H). Hafnium(2,3,4,5-tetramethyl [1-(3,5-di-tertbutylphenyl)]cyclopentadienyl)(tri(1-adamantyl)phosphiniminate) dichloride, (3,5-tBu2Ph-Me4Cp) (l-AdgPN) HfCl2 A solution of (3,5-tBu2Ph-Me4Cp)HfCl3 (1.934 g, 3.25 mmol) in toluene (30 mL) was added to a suspension of (1Ad)3P=NLi (1.48 g, 3.25 mmol) in toluene (30 mL) at -70°C. The suspension was stirred at -70°C for 5 minutes, and the cold bath was removed. The reaction was stirred at room temperature for 24 hours. The solution was filtered to remove the LiCl, and the filtrate was concentrated by vacuum pumping to approximately 2 mL. Two mL of pentane were added dropwise. The solution was left in a freezer at -35°C overnight, and the product crystallized. The mother liquor was pipetted. The solid was washed with cold toluene (-35°C, 2 x 5 mL), then with pentane (1 x 10 mL), and dried under vacuum. 2.50 g of highly crystalline solid were obtained. 3H NMR (toluene-dg, d, ppm): 7.61 (s, 2H), 7.40 (s, 1H), 2.53 (s, 6H), 2.28 (s, 6H), 2.47–2.18 (v.br.s, 18H), 1.87 (br.s, 10H), 1.77–1.53 (m, 17H), 1.39 (s, 18H). 3P NMR (toluene-dg, d, ppm): 29.4 (s). Dimethyl(2,3,4,5-tetramethyl[1-(3, 5-di-tert-butylphenyl)]cyclopentadienyl)(tri(1-adamantyl)phosphiniminate) hafnium, (3,5-tBu2Ph-Me4Cp) (l-AdgPN) HfMeg (3,5-tBu2Ph-Me4Cp) (l-AdgPN) HfCA (0.907 g, 0.9 mmol) was dissolved in toluene (125 mL). A solution of CHsMgBr (3 M in Et2O, 1.4 mL) was added to this solution. After stirring the reaction mixture for 2 hours, the solution became cloudy. Stirring continued overnight. The solution was pumped to remove the diethyl ether and filtered to remove the suspended solid. The filtrate was pumped to dryness. Toluene (50 mL) was added to dissolve the product. The solution was filtered to remove a small amount of solid, and the filtrate was pumped to dryness. The above process was repeated. A crystalline solid (0.460 g) was obtained after pumping the solution to dryness. NMR A (toluene-dg, d, ppm): 7.42 (br.s, 3H), 2.42 (s, 6H), 2.40 (br.s, 16H), 1.93 (br. 9H), 1.87 (br. m, 10H), 1.64 (dr.d, 10H), 1.41 (s, 18H) , 0.19 (s, 6H) . NMR31P (toluene-dg, d, ppm): 24.9 (s). Preparation of trans-2-methyl-2-butenoyl chloride A solution of oxalyl chloride (6.47 g, 51 mmol) in CH₂Cl₂ (40 mL) was added dropwise through a 20-gauge cannula to a solution of trans-2-methyl-2-butenoic acid (5.005 g, 50 mmol) in CH₂Cl₂ (30 mL). The addition took 20 minutes. Gas evolution was observed and vented through a 20-gauge cannula in the septum into a sodium hydroxide solution (4 M, ~200 mL). The reaction became cloudy and was stirred overnight while a small, constant stream of nitrogen flowed through the septum to the top of the reaction flask and then through a 20-gauge cannula into the sodium hydroxide solution. The CH₂Cl₂ was carefully distilled from the reaction flask. Pentane (30 ml) was added to the flask to dissolve the product. The undissolved solid (the starting material) was filtered out. The pentane was removed by distillation of the filtrate. The product was a clear liquid (which was used for the next reaction without weighing it).2H NMR (toluene-dg, d, ppm): 6.86 (qq, Ji = 7.0 Hz, J2= 1.3 Hz), 1.45 (pentet, J = 1.1 Hz, 3H), 1.18 (dq, Ji = 7.0 Hz, J2= 1.3 Hz). Preparation of 1,4-dihydro-l,2-dimethyl-4phenylcyclopent[b]indol-3(2H)-one N-Phenylindole (8.503 g, 44 mmol) prepared by the method reported in Syn. Leton. 2019, 30(11), 1313-1316 was dissolved in THF (150 mL). nBuLi (1.6 M, 28.3 mL) was added very slowly over 2 hours to this solution maintained at -13°C in an ethanol / dry ice bath. The cold bath was removed, and the reaction was stirred for 15 minutes and then cooled to -30°C in an ethanol / dry ice bath. A solution of ZnCl₂ in THF (80 mL) was added. The solution was stirred and warmed to room temperature in 40 minutes. A solution of Pd(PPh3)4 (1 mmol, 0.51 g) in THF (30 mL) was added through a cannula, followed by the addition of trans-2-methyl-2-butenoyl chloride (5.34 g, 45 mmol). The mixture was stirred overnight and pumped to dryness. The reaction residue was extracted with diethyl ether (4 x 200 mL), and the diethyl ether solution was washed with saturated NaCl solution (3 x 50 mL). The diethyl ether solution was dried with anhydrous MgSO4 and pumped to remove volatiles, yielding a thick oil. The thick oil was dissolved in CH₂Cl₂ (800 mL), and 0.260 g of CF₃SO₃H was added to 10 mL of CH₂Cl₂. The reaction was stirred for 1.5 hours, and the CH₂Cl₂ was removed using a rotary evaporator. The thick oil thus obtained was dissolved in pentane / diethyl ether (10:1, 200 mL). The solution was passed through a 45.72 cm (18 in) alumina column (f = 0.5), and the column was washed with an additional 600 mL of the mixed solvents. The volatiles in the filtrate were removed using a rotary evaporator to give an orange-colored oil. 3H NMR showed it to be 100% pure (two isomers, ratio -1:0.5, 11.0 g). NMR Y (toluene-dg, d, ppm): 7.727.64 (m, 1.5H), 7.49 (7.35 (m, 8H), 7.32-7.2 (m, 3H), 7.167.08 (m, 2H), 7.08-7.01 (m, 0.5H), 3.58 (pentet, J = 7 Hz, 0.5H), 3.08 (pentet, 0.5H), 3.02 (dq, Ji = 7 Hz, J2= 2.5 Hz, 1H), 2.48 (dq, Ji = 7 Hz, J2= 2.5 Hz, 1H), 1.47 (d, J = 7 Hz, 3H), 1.31 (d, J = 7 Hz, 1.5H), 1.26 (d, J = 7 Hz, 3H), 1.16 (d, J = 7 Hz, 1.5H). Preparation of 1,2,3-trimethyl-4-phenyl-1,4-dihydrocyclopent[b]indole CHgMgCl was added in THF (3.0 M, 10 ml) to a solution of 1,4-Dihydro-1,2-dimethyl-4-phenylcyclopent[b]indol-3(2H)-one (5.42 g, 19.68 mmol) was added to THF (100 mL). The reaction was heated to 58°C overnight. A large amount of solid precipitated. The suspension was carefully pipetted into 150 mL of aqueous HCl (total amount of HCl, 100 mmol) and the solution was stirred for 2 hours. The organic phase was separated, and the aqueous phase was extracted with diethyl ether (3 x 50 mL). The combined organic phases were washed with saturated NaCl solution (80 mL), dried with anhydrous MgSO4, and pumped to dryness. The thick oil was dissolved in pentane (-100 mL), the solution was passed through a 30.48 cm alumina column, f = 1.27 cm (12, f = 0.5), and rinsed with 400 mL of pentane. The filtrate was evaporated to dry, yielding a light orange oil (4.77 g). Note: The product decomposes in CDCi3 and with dry HCl. A NMR (acetone-dg, d, ppm): 7.65-7.57 (m, 3H), 7.57-7.48 (m, 4H), 7.13-7.10 (m, 1H), 7.09-7.05 (m, 1H), 6.98-6.93 (m, 1H), 2.00 (s, 3H), 1.68 (s, 3H), 1.38 (d, J = 7Hz, 3H). Preparation of 1,2,3-trimethyl-l-trimethylsilyl-4-phenyl-4hidrociclopent[b]indol To a stirred solution of 1,2,3-trimethyl-4-phenyl-1,4-dihydrocyclopent[b]indole (2.217 g, 8.11 mol) in diethyl ether (35 mL) was added benzyl potassium (1.06 g, 8.11 mmol). The orange-yellow suspension gradually turned red, and the benzyl potassium gradually disappeared. In approximately 40 minutes, all the benzyl potassium was gone. The solution became cloudy, and a red solid formed. The suspension was stirred for 2.5 hours and pumped to dryness. The solid was washed with pentane. The solid was dissolved in THF (40 mL) to form a very dark red solution. MegSiCl (1.2 g, 11 mmol, excess) in THF (10 mL) was added to the previous solution. The dark color disappeared, becoming almost colorless. The solution was left to stir overnight and pumped to dryness. The residue was extracted with pentane (50 mL) and the pentane solution was pumped to dryness to give the target product as a colorless oil (unweighed, used in the next step).RMNLH (CD2CI2, d, ppm): 7.58-7.52 (m, 3H), 7.47-7.40 (m, 3H), 1.21-7.17 (d, J = 7 Hz, 1H), 7.07 (t, J = 7 Hz, 1H), 7.01-6.96 (m, 1H), 2.00 (s, 3H), 1.72 (s, 3H), 1.58 (s, 3H), 0.05 (s, 9H). Preparation of 1,2,3-trimethyl-4-phenyl-4hydrocyclopent[b]indolylhafnium trichloride The 1,2,3-Trimethyl-l-trimethylsilyl-4-phenyl-4-hydrocyclopent[b]indole prepared in the last step in a 100 mL round-bottom flask was dissolved in toluene (40 mL). HfCl₁₄ (2.6 g, 8.1 mmol) was added to the flask from a hypovial. The mixture was heated to 90°C, the solution turned orange, and the HfCl₁₄ began to dissolve. After 0.5 hours, all the HfCl₁₄ had dissolved. The mixture was stirred at 79°C overnight. The toluene was removed by pumping, and the residue was extracted with dichloromethane (80 mL). An attempt to crystallize the product failed. The solvent was pumped to dryness, and 3.0 g of an orange solid were obtained. 4H NMR showed that this is the desired crude product. Dimethyl(1,2,3-trimethyl-4-phenyl-4hydrocyclopent[b]indolyl)(tri(1-adamantyl)phosphiniminate) hafnium To the orange solid from the last step (2.0 g, 3.58 mmol) in toluene (~40 mL) at -70°C, a suspension of (1Ad)3P=NLi was added. This suspension was prepared by adding nBuLi (2.28 mL) to (l-Ad)3P=NH (1.62 g, 3.58 mmol) in toluene (30 mL) and stirring overnight. The mixture was stirred and allowed to warm to room temperature. After stirring overnight, the solution was filtered to remove the LiCl through celite. This forms [1,2,3-trimethyl-4-phenyl-4-hydrocyclopent[b]indolyl](tri-l-adamantyl)hafnium dichloride. The solution was pumped to dryness and used for the next step. MeMgBr (3.0 M, 3.0 mL) in diethyl ether was added to a toluene solution of the solid from the last step. The solution was stirred overnight and pumped to dryness. The residue was extracted with pentane (~150 mL). The pentane extract was filtered to remove insoluble solids. The pentane filtrate was concentrated to 25 mL and cooled to -35°C; however, no crystals formed. However, once the solution was warmed to room temperature and allowed to stand for approximately 30 minutes, the product began to crystallize. After 3 hours, the mother liquors were decanted, and the white crystalline solid was washed with pentane (3 x 5 mL) and vacuum dried (0.63 g). NMR (toluene-dg, d, ppm): 7.85–7.78 (m, 1H), 7.51 (d, J = 7 Hz, 2H), 7.33-7.28 (m, 1H), 7.19 (t, J = 7 Hz, 2H), 7.15-7.06 (m, 2H), 7.06-7.0 (m, 1H), 2.66 (s, 3H), 2.40-2.29 (br.s, 18H), 2.28 (s, 3H), 2.18 (s, 3H), 1.92 (br.s, 9H), 1.79 (-1.55(m, 18H) , -0.120 (s, 3H), -0.229 (s, 3H) . RMN31P (tolueno-dg, d, ppm) : 24.78 (s) . In continuation, an alternative synthesis of higher yield of dimethyl(1,2,3-trimethyl-4-phenyl-4hidrocyclopent[b]indolyl) (tri(1adamantyl)fosphiniminate)hafnium is presented. Preparation of 1,2,3-trimethyl-4-phenyl-4hidrociclopent[b]indolylhaphnium trichloride nBuLi (1.6 M, 3.17 mL) was added to a solution of 1,2,3-trimethyl-4-phenyl-1,4-dihydrocyclopent[b]indole (1.389 g, 5.08 mmol) in diethyl ether (60 mL) in a 125 mL hypo vial at room temperature. A very thick suspension formed, which was stirred at room temperature for 1 hour. HfCA (1.627 g, 5.08 mmol) was weighed into a 300 mL Kontes flask and toluene (25 mL) was added. The flask was cooled to -70°C and the contents were stirred. Diethyl ether (-100 mL) was added slowly. The very thick suspension from the last reaction was transferred to the Schlenk flask. The vial was rinsed with diethyl ether (3 x 5 mL) and the washings were transferred to the Schlenk flask. The cold bath was removed, and the reaction was allowed to warm to room temperature. No apparent change was observed. The contents were stirred for 3 days. A yellow solution with a suspension of LiCl formed. The diethyl ether was removed by vacuum pumping, leaving a toluene solution of the product with a small amount of LiCl.The product was used without further insulation. Preparation of [1,2,3-trimethyl-4-phenyl-4hydrocyclopent[b]indolyl](tri(1-adamantyl)phosphiniminate) hafnium dichloride nBuLi (1.6 M, 3.33 mL) was added to (l-Ad)3P=NH (2.294 g, 5.08 mol) in toluene (~40 mL) at room temperature. The mixture was stirred at room temperature for 3 hours to form a suspension of (l-Ad)3P=NLi in toluene. This suspension was transferred to a Cp'HfCl3 solution at -70°C. The stirred suspension was heated to room temperature. After overnight stirring, the solid was filtered, and the filtrate was pumped to dryness. 3H and 3P NMR spectroscopy showed that the product (Cp')[(l-Ad)3PN]HfCl2 was pure. 3H NMR (CD2C12, d, ppm): 7.77 (d, J = 7 Hz, 1H), 7.67 (br.d, J = 7 Hz, 2H), 7.54 (t, J = 8 Hz, 2H), 7.41 (tt, J = 7 Hz, J = 1.3 Hz, 1H), 7.25 (d, J = 7 Hz, 1H), 7.20 (td, J = 7 Hz, J = 1.3 Hz, 1H), 7.11 (td, J = 7 Hz, J = 1.3 Hz, 1H), 2.79 (s, 3H), 2.40 (s,3H), 2.32 (br.s, 16H), 2.11 (s, 3H), 2.02 (br.s, 9H), 1.76 (br.m, 20Η). NMR31P (CD2C12, d, ppm): 30.9 (s). Preparation dimethyl(1,2,3-trimethyl-4-phenyl-4hydrocyclopent[b]indolyl)(tri(1-adamantyl)phosphiniminate)hafnium ινΐΛ / a / zuzz / ui / A solution of CHgMgBr (3.0 M, 3.0 mL) in diethyl ether was added to the solution from the previous reaction at room temperature. The solution was stirred overnight and pumped to dryness. The solid was extracted with pentane (3 x 80 mL). The pentane solution was pumped to dryness to give the target product (1.12 g). 3H NMR (toluene-dg, d, ppm): 7.83–7.78 (m, 1H), 7.51 (d, J = 7 Hz, 2H), 7.33–7.27 (m, 1H), 7.19 (t, J = 7 Hz, 2H), 7.15–7.06 (3, 2H), 7.06–7.0 (m, 1H) 2.66 (s, 3H), 2.40-2.29 (br.s, 18H), 2.28 (s, 3H), 2.18 (s, 3H), 1.92 (br.s, 9H), 1.79 (-1.55 (m, 18H), -0.127 (s, 3H), 0.233 (s, 3H). 31P NMR (toluene-dg, d, ppm): 24.84 (s). 1-Pentafluorobenzyl-2,3,4,5-tetramethylcyclopentadiene 1,2,3,4-Tetramethyl-1,3-cyclopentadiene (2 g, 16.37 mmol) was dissolved in a mixture of toluene (25 mL) and THF (25 mL). KN(TMS)₂ (3.27 g, 16.39 mmol) was added as a solid at room temperature. The mixture was stirred at room temperature for at least 3 hours and then added dropwise to a solution of 2,3,4,5,6-pentafluorobenzyl bromide (4.30 g, 16.35 mmol) in THF (80 mL) at -78°C. The reaction was heated to room temperature and stirred overnight. All volatiles were removed under vacuum, and the product was extracted with toluene (3 x 50 mL) and filtered through a Celite layer. The solvent from the combined filtrate was removed under vacuum and the product was obtained as a yellow liquid (4.5 g). 1-Pentafluorobenzyl-l-trimethylsilyl-2,3,4,5-tetramethyl cyclopentadiene The yellow liquid (4.5 g) was dissolved in toluene (80 mL) and a toluene solution of KN(TMS)₂ (3 g, 15.04 mmol) was added dropwise at room temperature. The reaction was stirred overnight. The precipitate (4 g) was collected by filtration, washed with pentane (3 x 5 mL), and dried under vacuum. The dried precipitate was dissolved in THF (60 mL) and chlorotrimethylsilane (3.52 g, 17.64 mmol) was added at room temperature. The reaction was stirred overnight. All volatiles were removed under vacuum, and the product was extracted with toluene (350 mL). After filtration, the solvent from the combined filtrate was removed under reduced pressure to give the product as a yellow liquid (2.5 g). Tribenzyl(1-pentafluorobenzyl-2,3,4,5-tetramethylcyclopentadienide)hafnium c6h5 The previously obtained product (2.5 g), HfC14 (2.14 g, 6.68 mmol), and toluene (50 mL) were mixed and heated to 90°C overnight. All solids dissolved, yielding a clear purple solution. After removing all volatiles under vacuum, the residue was dissolved in toluene (50 mL). Benzylmagnesium chloride (14.6 mL, 14.6 mmol, 1 M in Et2O) was added at room temperature. The reaction was stirred overnight, and all volatiles were removed under vacuum. Toluene (20 mL) was added to the residue. After stirring for 20 minutes, all volatiles were again removed under vacuum. This process was repeated three times. The product was then extracted with toluene (3 x 50 mL) and filtered through a layer of Celite. After removing all solvents from the combined filtrate, a yellow oil was obtained. The oil was dissolved in heptane (15 ml).The product was obtained as yellow crystals after placing the heptane solution at -35°C for several days. Yield: 4.9 g. 1H NMR (toluene-dg, δ, ppm): 7.30 (t, 6H), 7.07 (d, 3H), 6.80 (d, 6H), 3.55 (s, 2H), 2.05 (s, 6H), 1.95 (s, 6H), 1.86 (s, 6H). 19F NMR (toluene-dg, δ, ppm): -140.64 (d, 2F), -156.42 (t, 1F), -161.59 (dt, 2F). Dibenzyl(1-pentafluorobenzyl-2,3,4,5-tetramethylcyclopentadienide) (tri(1-adamantyl)phosphiniminate)hafnium ινΐΛ / a / zuzz / ui / Tribencil (1-pentafluorobenzyl-2,3,4,5-tetramethylcyclopentadienide) hafnium (2.3 g, 3.05 mmol) was dissolved in toluene (50 mL). Tri(1-adamantyl)phosphinimine (1.38 g, 3.05 mmol) was added as a solid. The mixture was stirred at room temperature for 3 hours. A clear yellow solution was formed. All volatiles were removed to give the desired product. The pure analytical product was obtained as a white solid by recrystallization from a toluene / heptane solution at -35°C. Yield: 2.7 g, 80%. NMR A (bromobenzene-dg, δ, ppm): 7.35 (t, 4H), 7.29 (d, 4H), 7.00 (t, 2H), 3.82 (s, 2H), 2.53 (br, 18H), 2.26 (s, 4H), 2.23 (s, 6H), 2.17 (br, 9H), 2.12 (s, 6H), 1.94 (d, 9H), 1.83 (d, 9H). NMR31P (bromobenzene-dj, δ, ppm): 28.34 (s). 19F NMR (bromobenzene-dg, δ, ppm): -140.68 (dd, 2F), -157.74 (t, 1F), -162.24 (dt, 2F). Preparation of potassium 1,2,3,4,5-pentapropylcyclopentadienide n-C3H7 1,2,3,4,5-Pentapropylcyclopentadiene (6.2 g, 22.4 mmol), prepared according to the procedure described in Chemistry - A European Journal 2002, 8(18), 4292-4298, was dissolved in toluene (20 mL). Potassium hexamethyldisilazide (4.483 g, 22.5 mmol) was dissolved in toluene (40 mL) and added to the mixture, which was stirred overnight, resulting in a precipitate. The solids were collected, rinsed with toluene (2 x 10 mL) and pentane (3 x 10 mL), and dried under reduced pressure. The product was used as is. Preparation of trimethyl(1,2,3,4,5-pentapropylcyclopenta2,4-dien-l-yl)silane n-C3H7 Potassium 1,2,3,4,5-pentapropylcyclopentadienide (0.749 g, 2.38 mmol) was suspended in THF (5 mL) in a vial. With vigorous shaking, chlorotrimethylsilane (0.33 mL, 2.62 mmol) was added. The reaction mixture was stirred overnight, resulting in a thick, creamy-yellow suspension. Volatiles were removed, yielding a paste. Extraction with pentane and filtration gave a yellow filtrate. Evaporation of the filtrate provided the desired product as a yellow oil (0.602 g, 1.73 mmol, 73% yield). RMNXH (toluene-dg, δ, ppm) : 2.50 - 2.10 (br, 10H, CH2CH2CH3), 1.80 - 1.40 (br, 10H, CH2CH2CH3), 1.10 - 0.80 (br, 15H, CH2CH2CH3), 0.00 (s, 9H, SiMe3) . Preparation of (pentapropylcyclopentadienyl)hafnium trichloride Trimethyl(1,2,3,4,5-pentapropylcyclopenta-2,4-dien-lyl)silane (1.969 g, 5.647 mmol) was diluted with toluene (50 mL) in a 10 mL round-bottom flask. Hafnium(IV) chloride (2.713 g, 8.470 mmol) was added, a condenser was placed, and the reaction mixture was heated at 95°C for 3 days. The dark reddish-brown mixture was filtered, and the filtrate was evaporated to dryness. The crude product was purified by recrystallization from toluene / heptane to give the desired product as a dark brown solid (2.353 g, 74% yield). NMR (toluene-dg, δ, ppm) : 2.60 (t, 10H, CH2CH2CH3) , 1.40 (sextet, 10H, CH2CH2CH3) , 0.87 (t, 15H, CH2CH2CH3) . Preparation of tribenyl(pentapropylcyclopentadienyl) hafnium (Pentapropylcyclopentadienyl)hafnium(IV) chloride (1.723 g, 3.075 mmol) was dissolved in toluene (12 mL). With vigorous stirring, benzylmagnesium chloride (12.30 mL of 1.0 M solution in Et₂O, 12.30 mmol) was added, resulting in a bright yellow suspension. After stirring for 4 hours, the volatiles were evaporated under reduced pressure to provide a sticky gel. Trituration with pentane yielded a solid residue. The residue was extracted with toluene and filtered. The filtrate was evaporated, resuspended in heptane, and the solids were collected and dried to give the desired product as bright yellow solids (0.969 g, 43% yield). Y NMR (toluene-dg, δ, ppm): 7.17 (t, 6H, m-ArH), 6.91 (t, 3H, p-ArH), 6.74 (d, 6H, o-AiH), 2.30 (m, 10H, CH2CH2CH3), 1.85 (s, 6H, CH2Ph), 1.55 (sextet, 10H, CH2CH2CH3), 0.98 (t, 15H, CH2CH2CH3). Preparation of dibenzyl(pentapropylcyclopentadienyl)(tri(1-adamantyl)phosphiniminate) hafnium Tribenzyl(pentapropylcyclopentadienyl)hafnium(IV) (1.061 g, 1.459 mmol) and tri(1-adamantyl)phosphinemine (0.659 g, 1.459 mmol) were suspended in toluene (15 mL) and stirred overnight. The mixture was diluted with toluene (50 mL), filtered, and the filtrate was concentrated to saturation at 60°C, cooled to room temperature, and stratified with pentane. The recrystallized product was recovered the following day (0.644 g, 41% recrystallized yield). NMR (toluene-dg, δ, ppm): 7.30-6.80 (m, 10H, CH2Ph), 2.60-1.50 (m, 54H, CH2CH2CH3& 1-Ad), 1.06 (t, 15H, CH2CH2CH3). Preparation of dibenzyl (cyclopentadienyl) (tri (1-adamantyl)phosphiniminate) zirconium Cyclopentadienylzirconium(IV) trichloride (0.672 g, 2.56 mmol) was suspended in Et2O (40 ml) and cooled to -30°C. Methylmagnesium bromide (2.84 ml of a 3.0 M solution in Et2O, 8.52 mmol) was added, providing a creamy yellow suspension. After stirring for 3 hours at -30°C, (l-AdAPNH) was added. The reaction mixture was heated to room temperature overnight. Volatiles were removed, the residue was extracted with toluene, filtered, and the filtrate was evaporated under reduced pressure. Repeated recrystallizations from chlorobenzene and pentane gave the desired product as a white solid (0.31 g, 19% recrystallized yield). A NMR (toluene-dg, δ, ppm): 66.38 (s, 5H, C5H5), 2.41 (br, 18H, 1-Ad), 1.96 (br, 9H, 1-Ad), 1.90-1.50 (m, 18H, 1-Ad), 0.33 (s, 6H, ZrMe2). WpH NMR (toluene-dg, δ, ppm) : 18.5 (s) . Continuous solution polymerization Continuous polymerizations were performed in a continuous polymerization unit (CPU) using cyclohexane as the solvent. The CPU contained a 71.5 mL stirred reactor and was operated between 130 and 190°C for the polymerization experiments. An upstream mixed reactor with a volume of 20 mL was operated at 5°C lower than the polymerization reactor. The mixed reactor was used to preheat the ethylene, octene, and some of the solvent streams. Catalyst supplies (xylene or cyclohexane solutions of the precatalyst complex (e.g., Cp*(1-AdgPN)HfCl2)) and (Ph3C)[B(C6F5)4] as catalyst activator and additional solvent were added directly to the polymerization reactor in a continuous process. Additional feeds of MMAO-7 with and without 2,6-di-tert-butyl-4-ethylphenol (BHEB) and solvent were also added to the polymerization reactor in a continuous process. Note that MAO refers to MMAO-7; MMAO-7 is a commercially available methylaluminoxane that reportedly contains some higher alkyl (C4-C6) substituents in addition to the methyl substituents. A total continuous flow rate of 27 mL / min was maintained in the polymerization reactor. The copolymers were prepared with octene / ethylene weight ratios ranging from 0.15 to 0.5. Ethylene was fed into the polymerization reactor at a concentration of 10 wt%. The CPU system operated at a pressure of 10.5 MPa. The solvent, monomer, and comonomer streams were all purified by the CPU systems before entering the reactor. The polymerization activity, kp (expressed in mM⁻¹ min⁻¹), is defined as: , = í—Me—V—1pV100- Q / VHUT> where Q is the ethylene conversion (%) (measured by an online gas chromatograph (GC)), [M] is the catalyst concentration in the reactor (mM) and HUT is the residence time in the reactor (2.6 min). Copolymer samples were collected with an ethylene (Q) conversion of 90±1%, dried in a vacuum oven, milled, and then analyzed by FTIR (for short-chain branching frequency) and GPC-RI (for molecular weight and distribution). The polymerization results are summarized in Tables 1-3 below. Polymerization results The results shown in Table 1 are all comparative (Comparative Examples 1 to 7) because the phosphinimine ligand of the catalyst used in these experiments does not have an adamantyl moiety. TABLE 1 Impact of Scrubber on Catalyst Cp* (tBu3PN) Hf (CH2Ph)2ινΐΛ / a / zuzz / ui / Examples (Comparative) Temp. (°C) Al / Hf Scrubber (mol / mol) BHEB / Al (mol / mol) Activity % Ethylene Conversion Comp. 1 160 MAO / BHEB 39.75 0.30 5936 89.14 Comp. 2 160 MAO / BHEB 37.50 0.30 6106 89.41 Comp. 3 160 MAC only 18.00 - 3280 90.43 Comp. 4 140 TIBAL 9.00 - 1327 88.43 Comp. 5 160 TEAL 37.5 - 45 5.81 Comp. 6 190 TEAL 4.78 - 7 7.3 Comp. 7 190 TEAL 14.34 - 10 9.9 Note 1: The 1-octene / ethylene ratio was 0.3 w / w for Examples 1-5; no 1-octene was added to the reactor for Examples 6-7. The molar ratio (PhsC)[B(CeF5)4] / Hf was 1.2 for Examples 1-5 and 2.0 for Examples 6-7; TIBAL = triisopropyl aluminum; TEAL = triethylaluminum; BHEB = 2,6-di-tert-butyl-4-ethylphenol; Cp* = pentamethylcyclopentadienyl. Comparative Examples 1 and 2 show that the catalyst Cp*(tBugPN)Hf(CXPh)2 had moderate activity (kp of 5936 and 6106, respectively) at 160°C when MAO / BHEB was used as the scrubber. When BHEB was removed while using MAC as the scrubber, as in Comparative Example 3, the activity dropped sharply to a kp of 3280. When simple aluminum alkyls (TIBAL, TEAL) were used as scrubbers (Comparative Examples 4–7), the catalyst had low or almost no activity at both 160°C and 160°C and 190°C. TABLE 2 Polymerization results with Cp* catalyst (l-AdgPN) ΗίΜθ2^ Example (Inventive) Temp. (°C) Scrubber 1-C8 / C2 (w / w) Al / Hf (mol / mol) BHEB / Hf (mol / mol) BHEB / Al (mol / mol) Activity % Ethylene Conversion 1 190 MAO 0.15 80 8 0.1 10158 89.8 2 190 MAO 0.5 80 8 0.1 9973 89.63 3 160 MAO 0.5 80 8 0.1 21520 89.91 Note 2: The (PhaC) [B (CgFs) 4] / Hf ratio was 1.2; 1-octene (1-C8) / ethylene (C2) ratio; BHEB = 2,6-di-tert-butyl-4-ethylphenol; 1-Ad = 1-adamantyl; Cp* = pentamethylcyclopentadienyl. TABLE 3 Polymerization results with catalyst Cp*(lAd3PN)Hf(CH2Ph)23 Example (Inventive) Temp. (°Q) Scrubber (Ph3C)[B(C6F5)4] / Hf (mol / mol) 1-C8 / C2 (w / w) Al / Hf (mol / mol) BHEB / Hf (mol / mol) 4 160 MAO 1.20 0.5 80 24 5 160 MAO 1.20 0.5 80 0 6 160 MAO 1.20 0.5 4.98 0 7 190 MAO 1.20 0.5 5.01 0 8 160 TnOAl 1.12 0.5 4.73 0 9 160 Et2AlOEt 1.12 0.5 3.54 0 TABLE 3 - CONTINUED Polymerization results with catalyst Cp*(1Ad3PN) Hf (CH2Ph)23 Example (Inventive) BHEB / AI (mol / mol) Activity (kP) Ethylene Conversion (%) SCB / 1000C Mw PD (Mw / Mn) 4 0.3 20,950 90.32 12.0 31,082 1.91 5 0.0 16,736 90.26 13.3 29,509 1.90 6 0.0 18,462 90.11 12.6 30,758 1.84 7 0.0 12,932 92.11 12.6 19,180 1.93 8 0.0 11,560 89.95 11.6 32,499 1.91 9 0.0 8,136 89.36 10.8 33,941 1.77 Note 3: 1-octene = 1-C8; ethylene = C2; BHEB = 2,6-di tert-butyl-4-ethylphenol; TnOAl = tri(n-octyl)aluminum; 1-Ad = 1-adamanti lo; Cp* = pentamethylcyclopentadienyl. Table 2 shows that at 160°C, the catalyst Cp*(lAd3PN)HfMe2 reached extremely high activity with a kp of 21520 (Example Inv. 3) with MAO as a scrubber with 0.1 BHEB equivalents. When the polymerization temperature was increased to 190°C (Examples Inv. 1 and 2), the catalyst activity was still very high with a kp of 10158 and 9973, respectively. Table 3 shows the polymerization results with the catalyst Cp*(l-Ad3PN) Hf (CH2Ph)2 which has different activatable ligands compared to Cp* (l-Ad3PN)HfMe2. At 160°C, in the presence of scrubber (MAO / BHEB), the catalyst system achieved extremely high activity with a kp of 20950 (Example Inv. 4). At the same temperature (Example Inv. 5), while using only MAO as a scrubber (i.e., without the use of bulky phenol BHEB), the catalyst system still achieved very high activity with a kpde of 16763. When the Al / Hf ratio was decreased from 80 to 4.98 (Example Inv. 6), very high activity was still achieved, with a kpde of 18462. Even at 190°C (Example Inv. 7), the catalyst activity was still very high with a kpde of 12932.Finally, when the polymerization was carried out using simple aluminum alkyls as a scrubber, such as TnOAl and Et2AlOEt, and in the absence of BHEB, the catalyst activity was still very high with kp values ​​greater than 8000 (Examples Inv. 8 and 9). Tables 4 and 5 report further polymerization results using additional derivatives of catalytic complexes having a cyclopentadienthyl ligand and a phosphinimine ligand bearing an adamantyl moiety (including substituted and unsubstituted adamantyl moiety). Additional hafnium-based complexes and their polymerization results are provided in Table 4, while zirconium-based complexes and their polymerization results are provided in Table 5. The polymers were prepared using a continuous solution polymerization process in a CPU unit as previously described. TABLE 4 Polymerization results with other hafnium catalysts 1-adamantylphosphinimine4 Example, Complex (Inventive) Temp. (°C) Activator Al / Hf (mol / mol) BHEB / AI (mol / mol) C8 / C2 (P / P) 10, Cp*((1-Ad')2(1-Ad)PN)HfBn2 140 [Ph3C][B(C6F5)4] 45 0.3 0.15 11, Cp*((1-Adj2(1-Ad)PN)HfBn2 140 [Ph3C][B(C6F5)4] 43 0.3 0.30 12, Cp*((1-Adj2(1-Ad)PN)HfBn2 140 [Ph3C][B(C6F5)4] 43 0.3 0.50 13, Cp*((1-Adj2(1-Ad)PN)HfBn2 140 [Ph3C][B(C6F5)4] 45 0 0.50 14, Cp*((1-Adj2(1-Ad)PN)HfBn2 190 [Ph3C][B(C6F5)4] 25 0.3 0 15, Cp*((1-Adj2(1-Ad)PN)HfBn2 190 [Ph3C][B(C6F5)4] 28 0.3 0.15 16, Cp*((1-Adj2(1-Ad)PN)HfBn2 190 [Ph3C][B(C6F5)4] 25 0.3 0.50 18, (3,5-íBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 140 [Ph3C][B(C6F5)4] 62 0.3 0.15 19, (3,5-íBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 140 [Ph3C][B(C6F5)4] 62 0.3 0.30 20, (3,5-íBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 140 [Ph3C][B(C6F5)4] 54 0.3 0.50 21, (3.5-tBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 140 [Ph3C][B(C6F5)4] 48 0 0.50 22, (3,5-íBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 190 [Ph3C][B(C6F5)4] 43 0.3 0 23, (3,5-íBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 190 [Ph3C][B(C6F5)4] 43 0.3 0.15 24, (3,5-fBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 190 [Ph3C][B(C6F5)4] 43 0.3 0.30. 25, (3,5-fBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 190 [Ph3C][B(C6F5)4] 54 0.3 0.50 26, [(C6F5CH2)(CH3)4Cp]((1Ad)3P=N)HfBn2 140 [Ph3C][B(C6F5)4] 48 0.3 0.00 27, [(C6F5CH2)(CH3)4Cp]((1- Ad)3P=N)HfBn2 140 [Ph3C][B(C6F5)4] 48 0.3 0.15 28, [(C6F5CH2)(CH3)4Cp]((1Ad)3P=N)HfBn2 140 [Ph3C][B(C6F5)4] 43 0.3 0.30 29, [(C6F5CH2)(CH3)4Cp]((1Ad)3P=N)HfBn2 140 [Ph3C][B(C6F5)4] 43 0.3 0.50 30, [(C6F5CH2)(CH3)4Cp]((1Ad)3P=N)HfBn2 140 [Ph3C][B(C6F5)4] 54 0 0.50 31, [(C6F5CH2)(CH3)4Cp]((1Ad)3P=N)HfBn2 140 B(C6F5)3 0.96 0.3 0.30 32, [(C6F5CH2)(CH3)4Cp]((1Ad)3P=N)HfBn2 190 [Ph3C][B(C6F5)4] 19.29 0.3 0.00 33, [(C6F5CH2)(CH3)4Cp]((1- Ad)3P=N)HfBn2 190 [Ph3C][B(C6F5)4] 20.77 0.3 0.15 34, [(C6F5CH2)(CH3)4Cp]((1Ad)3P=N)HfBn2 190 [Ph3C][B(C6F5)4] 22.50 0.3 0.30 35, [(C6F5CH2)(CH3)4Cp]((1Ad)3P=N)HfBn2 190 [Ph3C][B(C6F5)4] 20.77 0.3 0.50 36, n-Pr5Cp((1-Ad)3PN)HfBn2 140 [Ph3C][B(C6F5)4] 13.50 0.3 0.00 37, n-Pr5Cp((1-Ad)3PN)HfBn2 140 [Ph3C][B(C6F5)4] 13.50 0.3 0.15 38, n-Pr5Cp((1-Ad)3PN)HfBn2 140 [Ph3C][B(C6F5)4] 13.50 0.3 0.30 39, n-Pr5Cp((1-Ad)3PN)HfBn2 140 [Ph3C][B(C6F5)4] 13.50 0.3 0.50 40, n-Pr5Cp((1-Ad)3PN)HfBn2 140 [Ph3C][B(C6F5)4] 14.59 0 0.50 41, n-Pr5Cp((1-Ad)3PN)HfBn2 140 B(C6F5)3 0.89 0.3 0.30 42, n-Pr5Cp((1-Ad)3PN)HfBn2 190 [Ph3C][B(C6F5)4] 2 0.3 0.00 43, n-Pr5Cp((1-Ad)3PN)HfBn2 190 [Ph3C][B(C6F5)4] 2 0.3 0.15. 44, n-Pr5Cp((1-Ad)3PN)HfBn2 190 [Ph3C][B(C6F5)4] 2 0.3 0.30 45, n-Pr5Cp((1-Ad)3PN)HfBn2 190 [Ph3C][B(C6F5)4] 2 0.3 0.50 46, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 140 [Ph3C][B(C6F5)4] 48 0.3 0.00 47, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 140 [Ph3C][B(C6F5)4] 43.20 0.3 0.15 48, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 140 [Ph3C][B(C6F5)4] 43.20 0.3 0.30 49, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 140 [Ph3C][B(C6F5)4] 36 0.3 0.50 50, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 140 [Ph3C][B(C6F5)4] 36 0 0.50 51, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 140 B(C6F5)3 3.38 0.3 0.30 52, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 190 [Ph3C][B(C6F5)4] 15.43 0.3 0.00 53, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 190 [Ph3C][B(C6F5)4] 15.43 0.3 0.15 54, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 190 [Ph3C][B(C6F5)4] 15.43 0.3 0.30 55, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 190 [Ph3C][B(C6F5)4] 15.43 0.3 0.50 56, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 190 [Ph3C][B(C6F5)4] 15.43 0 0.5. Note 4: Debugger = MAO; the Al concentration in the reactor was 20 umol / L; molar ratio [Ph3C] [B (CgF5)4] / Hf = 1.2; molar ratio B(CeF5)3 / Hf = 1.2; BHEB = 2,6-di-tert-butyl-4ethylphenol; (Ph-indolyl)(l,2,3-Me3Cp = 1,2,3-trimethyl-4-phenyl4-hydrocyclopent[b]indolyl; 1-Ad = 1-adamantyl; 1-Ad' =3.5 ινΐΛ / a / zuzz / ui / Meg-l-Ad, Cp* = pentamethylcyclopentadienyl. TABLE 4 - CONTINUED Polymerization results with other hafnium catalysts 1-adamanti1phosph inimine4 Ejamplo, Complejo (Inventivo) Conversión de Fileno (%) Actividad (kP) SCB / 1000C Mw PD Mw / Mn 10, Cp*((1-Adj2(1-Ad)PN)HfBn2 90.14 7,995 11,Cp*((1-Adj2(1-Ad)PN)HfBn2 90.44 7,859 12, Cp*((1-Adj2(1-Ad)PN)HfBn2 89.34 6,963 12.3 41,573 2.02 13, Cp*((1-Adj2(1-Ad)PN)HfBn2 90.49 8,321 14, Cp*((1-Adj2(1-Ad)PN)HfBn2 90.53 4,672 0.6 27,144 1.98 15, Cp*((1-Adj2(1-Ad)PN)HfBn2 89.31 4,507 3.2 25,998 2.24 16, Cp*((1-Adj2(1-Ad)PN)HfBn2 89.67 4,683 6 24,731 2.04 17, Cp*((1-Adj2(1-Ad)PN)HfBn2 90.20 4,498 9.5 23,142 2.12 18, (3,5-tBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 90.60 11,439 19, (3,5-íBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 89.3 9,905 20, (3,5-tBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 90.2 9,558 16.4 50,712 1.82 21, (3,5-tBu2-Ph-Me4Cp)((1- Ad)3PN)HfMe2 89.75 8,083 22, (3,5-íBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 89.08 6,777 1.3 32,740 2.07 23, (3,5-íBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 89.63 7,181 4.2 28,528 1.89 24, (3,5-íBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 90.03 7,502 7.9 26,289 1.9 25, (3,5-fBu2-Ph-Me4Cp)((1Ad)3PN)HfMe2 90.92 10,398 11.6 22,719 1.9 26, [(C6F5CH2)(CH3)4Cp]((1- Ad)3P=N)HfBn2 89.79 8,118 <0.5 49,053 1.84 27, [(C6F5CH2)(CH3)4Cp]((1Ad)3P=N)HfBn2 89.02 7,484 4.2 44,126 1.72 28, [(C6F5CH2)(CH3)4Cp]((1- Ad)3P=N)HfBn2 90.7 8,102 8.9 37,739 1.89 29, [(C6F5CH2)(CH3)4Cp]((1- Ad)3P=N)HfBn2 90.37 7,796 13.7 34,292 1.93 30, [(C6F5CH2)(CH3)4Cp]((1- Ad)3P=N)HfBn2 89.21 8,586 13.2 35,813 1.89 31, [(C6F5CH2)(CH3)4Cp]((1- Ad)3P=N)HfBn2 89.4 156 5.9 36,873 2.12 32, [(C6F5CH2)(CH3)4Cp]((1- Ad)3P=N)HfBn2 90.27 3,441 1.8 12,510 2.43 33, [(C6F5CH2)(CH3)4Cp]((1- Ad)3P=N)HfBn2 90.31 3,722 4.9 13,376 2.17 34, [(C6F5CH2)(CH3)4Cp]((1- Ad)3P=N)HfBn2 89.63 3,740 7.1 13,604 2.03 35, [(C6F5CH2)(CH3)4Cp]((1- Ad)3P=N)HfBn2 90.55 3,827 12.1 11,781 3.43 36, n-Pr5Cp((1-Ad)3PN)HfBn2 89.40 2,190 <0.5 58,756 1.74 37, n-Pr5Cp((1-Ad)3PN)HfBn2 89.76 2,276 4.7 53,406 1.77 38, n-Pr5Cp((1-Ad)3PN)HfBn2 90.45 2,459 9.7 50,981 2.37 39, n-Pr5Cp((1-Ad)3PN)HfBn2 90.94 2,606 15.1 48,566 1.7. 40, n-Pr5Cp((1-Ad)3PN)HfBn2 90.38 2,637 15.6 49,385 1.85 41, n-Pr5Cp((1-Ad)3PN)HfBn2 89.33 143 8.2 66,457 1.72 42, n-Pr5Cp((1-Ad)3PN)HfBn2 89.28 333 0.8 29,275 2.00 43, n-Pr5Cp((1-Ad)3PN)HfBn2 89.4 337 4.1 27,045 1.89 44, n-Pr5Cp((1-Ad)3PN)HfBn2 89.48 340 6.5 24,177 2.39 45, n-Pr5Cp((1-Ad)3PN)HfBn2 89.53 342 10.4 24,495 1.97 46, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 90.08 8,382 1.5 35,141 2.03 47, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 90.15 7,603 8.5 29,802 2.16 48, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 89.41 7,014 13.2 26,483 2.07 49, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 90.25 6,408 20.4 23,516 2.17 50, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 90.32 6,460 21.6 20,524 2.47 51,[(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 90.1 591 13.3 31,165 2.02 52, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 90.75 2,911 53, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 90.50 2,826 54, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 90.48 2,820 55, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 90.50 2,826 56, [(Ph-lndolyl)(1,2,3-Me3Cp)]((1- Ad)3P=N)HfMe2 89.73 2,592. Note 4: Debugger = MAO; The Al concentration in the reactor was 20 umol / L; molar ratio [Ph3C] [B (CeF5)4] / Hf = 1.2; molar ratio B(CgF5)3 / Hf = 1.2; BHEB = 2,6-di-tert-butyl-4ethylphenol; (Ph-indolyl)(l,2,3-Me3Cp = 1,2,3-trimethyl-4-phenyl4-hydrocyclopent[b]indolyl; 1-Ad = 1-adamantyl; 1-Ad' =3,5 Me2-1-Ad, Cp* = pentamethylcyclopentadienyl. TABLE 5 Results of polymerization with zirconium catalysts 1adamantylphosphinemin5 Example, Complex (Inventive) Temp. (°C) Activator Al / Zr (mol / mol) BHEB / Al (mol / mol) C8 / C2 (w / w) 57, Cp*((1-Ad')2(1-Ad)PN)Zr(CH2Ph)2 140 [Ph3C][B(C6F5)4] 66 0.3 0.15 58, Cp*((1-Ad')2(1-Ad)PN)Zr(CH2Ph)2 140 [Ph3C][B(C6F5)4] 64 0.3 0.30 59, Cp*((1-Ad')2(1-Ad)PN)Zr(CH2Ph)2 140 [Ph3C][B(C6F5)4] 64 0.3 0.50 60, Cp*((1-Ad')2(1-Ad)PN)Zr(CH2Ph)2 140 B(C6F5)3 13.5 0.3 0.30 61, Cp*((1-Ad')2(1-Ad)PN)Zr(CH2Ph)2 190 [Ph3C][B(C6F5)4] 36 0.3 0 62, Cp*((1-Ad')2(1-Ad)PN)Zr(CH2Ph)2 190 [Ph3C][B(C6F5)4] 36 0.3 0.15 63, Cp*((1-Ad')2(1-Ad)PN)Zr(CH2Ph)2 190 [Ph3C][B(C6F5)4] 36 0.3 0.30 64, Cp*((1-Ad')2(1-Ad)PN)Zr(CH2Ph)2 190 [Ph3C][B(C6F5)4] 54 0.3 0.50 65, Cp*((1-Ad)3PN)Zr(CH2Ph)2 140 [Ph3C][B(C6F5)4] 98 0.3 0.15 66, Cp*((1-Ad)3PN)Zr(CH2Ph)2 140 [Ph3C][B(C6F5)4] 83 0.3 0.30 67, Cp*((1-Ad)3PN)Zr(CH2Ph)2 140 [Ph3C][B(C6F5)4] 65 0.3 0.50 68, Cp*((1-Ad)3PN)Zr(CH2Ph)2 140 B(C6F5)3 48 0.3 0.30 69, Cp*((1-Ad)3PN)Zr(CH2Ph)2 190 [Ph3C][B(C6F5)4] 47 0.3 0 70, Cp*((1-Ad)3PN)Zr(CH2Ph)2 190 [Ph3C][B(C6F5)4] 51 0.3 0.15 71, Cp*((1-Ad)3PN)Zr(CH2Ph)2 190 [Ph3C][B(C6F5)4] 49 0.3 0.30. 72, Cp*((1-Ad)3PN)Zr(CH2Ph)2 190 [Ph3C][B(C6F5)4] 68 0.3 0.50 73, Cp*((1-Ad)3PN)Zr(CH2Ph)2 190 [Ph3C][B(C6F5)4] 47 0.3 0.50 74, Cp((1-Ad)3PN)ZrMe2 140 [Ph3C][B(C6F5)4] 54.00 0.3 0.00 75, Cp((1-Ad)3PN)ZrMe2 140 [Ph3C][B(C6F5)4] 33.23 0.3 0.15 76, Cp((1-Ad)3PN)ZrMe2 140 [Ph3C][B(C6F5)4] 12.71 0.3 0.30 77, Cp((1-Ad)3PN)ZrMe2 140 [Ph3C][B(C6F5)4] 5.40 0.3 0.50 78, Cp((1-Ad)3PN)ZrMe2 190 [Ph3C][B(C6F5)4] 3.38 0.3 0.00 79, Cp((1-Ad)3PN)ZrMe2 190 [Ph3C][B(C6F5)4] 2.88 0.3 0.15 80, Cp((1-Ad)3PN)ZrMe2 190 [Ph3C][B(C6F5)4] 2.70 0.3 0.30 81, Cp((1-Ad)3PN)ZrMe2 190 [Ph3C][B(C6F5)4] 2.40 0.3 0.50 ινΐΛ / a / zuzz / u i / Note 5: Scrubber = MAC; The concentration of Al in the reactor was 20 µmol / L; molar ratio [Ph3C] [B (C6F5)4] / Zr = 1.2; molar ratio B(C6F5)3 / Zr = 1.2; BHEB = 2,6-di-tert-butyl-4-ethylphenol; 1-Ad = 1-adamantyl; 1-Ad' = 3, 5-Me2-l-Ad, Cp* = pentamethylcyclopentadienyl; Cp = cyclopentadienyl. TABLE 5 - CONTINUED Results of polymerization with zirconium catalysts 1adamantylphosphinemin5 Example, Complex (Inventive) Ethylene Conversion (%) Activity (kP) SCB / 1000C Mw PD Mw / Mn 57, Cp*(( 1 -Ad')2( 1 -Ad) PN )Zr(CH2Ph)2 90.43 12,077 1.4 33,461 2.2 58, Cp*(( 1 -Ad j2(1 -Ad)PN)Zr(CH2Ph)2 90.65 11,933 3.4 28,982 2.04 59, Cp*(( 1 -Adj2( 1 -Ad)PN)Zr(CH2Ph)2 90.01 11,089 5.5 25,420 1.9 60, Cp*(( 1 -Ad j2(1 -Ad)PN)Zr(CH2Ph)2 90.27 2,409 3.1 25,432 1.86 61, Cp*((1-Adj2(1-Ad)PN)Zr(CH2Ph)2 90.27 6,423 <0.5 18,055 1.94 100 62, Cp*((1-Adj2(1-Ad)PN)Zr(CH2Ph)2 89.50 5,901 1.3 17,576 1.88 63, Cp*((1-Adj2(1-Ad)PN)Zr(CH2Ph)2 90.18 6,358 2.7 16,826 1.76 64, Cp*((1-Adj2(1-Ad)PN)Zr(CH2Ph)2 90.53 9,927 4.4 14,732 2.01 65, Cp*((1-Ad)3PN)Zr(CH2Ph)2 89.50 16,094 66, Cp*((1-Ad)3PN)Zr(CH2Ph)2 90.3 14,873 67, Cp*((1-Ad)3PN)Zr(CH2Ph)2 91.38 13,344 n / a n / a n / a 68, Cp*((1-Ad)3PN)Zr(CH2Ph)2 90.36 8,652 3.2 29,233 1.98 69, Cp*((1-Ad)3PN)Zr(CH2Ph)2 90.78 8,891 <0.5 18,297 2.02 70, Cp*((1-Ad)3PN)Zr(CH2Ph)2 90.29 9,196 1.3 17,572 1.7 71, Cp*((1-Ad)3PN)Zr(CH2Ph)2 90.73 9,240 3.6 16,915 1.89 72, Cp*((1-Ad)3PN)Zr(CH2Ph)2 89.31 10,854 4.5 16,483 1.9 73, Cp*((1-Ad)3PN)Zr(CH2Ph)2 90.12 8,237 4.3 16,832 1.89 74, Cp((1-Ad)3PN)ZrMe2 90.38 9,756 75, Cp((1-Ad)3PN)ZrMe2 89.38 5,378 76, Cp((1-Ad)3PN)ZrMe2 89.00 1,977 77, Cp((1-Ad)3PN)ZrMe2 89.00 840 78, Cp((1-Ad)3PN)ZrMe2 89.31 542 2.8 15,302 4.11 79, Cp((1-Ad)3PN)ZrMe2 89.61 478 6.7 10,291 3.5 80, Cp((1-Ad)3PN)ZrMe2 89.51 443 9.5 7,354 2.9 81, Cp((1-Ad)3PN)ZrMe2 89.90 411 15.3 5,524 3.2 Note 5: Scrubber = MAO; The concentration of Al in the reactor was 20 µmol / L; molar ratio [PhaC] [B (CgF5)4] / Zr = 1.2; molar ratio BÍCgFsH / Zr = 1.2; BHEB = 2,6-di-tert-butyl-4-ethylphenol; 1-Ad = 1-adamantyl; 1-Ad' = 3,5-Me2~lAd, Cp* = pentamethylcyclopentadienyl; Cp = cyclopentadienyl. The data provided in Tables 4 and 5 show that 101 More complexes based on hafnium and zirconium having a cyclopentadienyl-type ligand and a phosphinimine ligand carrying an unsubstituted or substituted adamantil moiety can be employed in active olefin polymerization catalyst systems, in olefin polymerization processes such as a solution-phase olefin polymerization process. The non-limiting modalities of this description include the following: Modality A. A complex number that has the formula (PI) (Cp)ML2, where: I) PI is a phosphinemine ligand defined by the formula: R1' R1— P=NR1 where N is a nitrogen atom; P is a phosphorus atom; each R1 is either unsubstituted adamantyl or substituted adamantyl; and R1' is selected from the group consisting of unsubstituted adamantyl, substituted adamantyl, and hydrocarbyl C ia C g; II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered carbon ring having a delocalized bond within the ring and bonding to M, whose 102 rings are not replaced or may be additionally replaced; III) each L is an activatable ligand; and IV) M is zirconium or hafnium. Modality B. The complex according to Modality A where R1' is unsubstituted adamantyl or substituted adamantyl. Modality C. The complex according to Modality A where R1' is unsubstituted adamantyl. Modality D. The complex according to Modality A, B or C where each R1 is unsubstituted adamantyl. Modality E. The complex according to Modality A where R1' and each R1 is 1-adamantile. Modality F. The complex according to Modality A, B, C, D or E where Cp is (pentamethyl)cyclopentadienyl. Modality G. The complex according to Modality A, B, C, D or E where Cp is cyclopentadienyl. Modality H. The complex according to Modality A, B, C, D, E, F or G where M is zirconium. Modality I. The complex according to Modality A, B, C, D, E, F or G where M is hafnium. Modality J. An olefin polymerization catalyst system comprising: A) a complex having the formula (PI)(Cp)ML2, where: I) PI is a phosphinimine ligand defined by the 103 formula: R1' R1— P=NR1 where N is a nitrogen atom; P is a phosphorus atom; each R1 is either unsubstituted adamantyl or substituted adamantyl; and R1' is selected from the group consisting of unsubstituted adamantyl, substituted adamantyl, and hydrocarbyl C ia C g; II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered carbon ring having a delocalized bond within the ring and bonding to M, whose rings are either unsubstituted or may be further substituted; III) each L is an activatable ligand; and IV) M is zirconium or hafnium; and B) an activator. Modality K. The olefin polymerization catalyst system according to Modality I, wherein the activator is selected from the group consisting of an aluminoxane; an organoaluminum compound; an ionic activator; and mixtures thereof. Mode L. The olefin polymerization catalyst system according to Mode J or K, wherein R1' is unsubstituted adamantyl or substituted adamantyl. 104 Mode M. The olefin polymerization catalyst system according to Mode J or K, wherein R1' is unsubstituted adamantyl. Modality N. The olefin polymerization catalyst system according to claim J, K, L or M, wherein each R1 is unsubstituted adamantyl. Mode O. The olefin polymerization catalyst system according to claim J or K, wherein R1' and each R1 is 1-adamantile. Mode P. The olefin polymerization catalyst system according to Mode J, K, L, M, N or O, wherein Cp is (pentamethyl)cyclopentadienyl. Mode Q. The olefin polymerization catalyst system according to Mode J, K, L, M, N or O, wherein Cp is cyclopentadienyl. Mode R. The olefin polymerization catalyst system according to Mode J, K, L, M, N, O, P or Q, wherein M is zirconium. Mode S. The olefin polymerization catalyst system according to Mode J, K, L, M, N, O, P or Q, wherein M is hafnium. Mode T. A process for the polymerization of olefins comprising contacting one or more ethylene and C3a C10 alpha olefins with the olefin polymerization catalyst system according to any of the 105 claims Modality J, K, L, M, N, O, P, Q, R or S under polymerization conditions. Modality U. The process according to Modality T wherein one or more of ethylene and C3 to C10 alpha olefins consist of a) ethylene; and b) one or more olefins selected from the group consisting of 1-butene; 1-hexene; and 1-octene. Mode V. A process for the (co)polymerization of ethylene comprising: A) preparing a first polymer solution by polymerizing ethylene, optionally with one or more C3 to C10 alpha olefins, in a solvent in a first polymerization reactor at a temperature of 80 to 200°C and a pressure of 6894.76 kPa to 55,158.07 psi (1000 to 8000 psi) in the presence of (i) the complex according to Modality A; and (ii) an activator consisting essentially of an aluminoxane and an ionic activator; and B) passing the first polymer solution to a second polymerization reactor and (co)polymerizing ethylene, optionally with one or more C3-C10 alpha olefins, in the presence of a Ziegler Naphtha catalyst. Mode W. A process for the (co)polymerization of ethylene comprising: A) Prepare a first polymer solution by polymerizing ethylene, optionally with one or more C3 to C10 alpha olefins, in a solvent in a first polymerization reactor at a temperature of 80 to 200°C and a pressure of 6894.76 kPa 55,158.07 (1000 to 8000 psi) in the presence of (i) the complex according to Modality A; and (ii) an activator consisting essentially of an organoaluminum compound and an ionic activator; and B) passing the first polymer solution to a second polymerization reactor and (co)polymerizing ethylene, optionally with one or more alpha C3-C10 polymers, in the presence of a Ziegler Natta catalyst. INDUSTRIAL APPLICABILITY Zirconium and hafnium complexes are provided that have a cyclopentadienyl ligand and a phosphinimine ligand bearing an adamantyl moiety (substituted or unsubstituted). The new complexes are active in the polymerization of ethylene with an alpha olefin. It is hereby stated that, with regard to this date, the best method known to the applicant to put the aforementioned invention into practice is the one that is clear from the present description of the invention.

Claims

1. A complex having the formula (PI)(Cp)ML2, characterized in that: I) PI is a phosphinimine ligand defined by the formula: R1' R1 — P=NR1 where N is a nitrogen atom; P is a phosphorus atom; each R1 is unsubstituted or substituted adamantyl; and R1' is selected from the group consisting of unsubstituted adamantyl, substituted adamantyl and hydrocarbyl C ia C g; II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered carbon ring having a delocalized bond within the ring and bonded to M, the ring of which is unsubstituted or may be further substituted; III) each L is an activatable ligand; and IV) M is zirconium or hafnium.

2. The complex according to claim 1, characterized in that R1' is unsubstituted adamantyl or substituted adamantyl.

3. The complex according to claim 1, characterized in that R1' is unsubstituted adamantyl.

4. The complex according to claim 3, characterized in that each R1 is unsubstituted adamantyl.

5. The complex according to claim 4, characterized in that R1' and each R1 is 1-adamantile.

6. The complex according to any of claims 1-5, characterized in that Cp is (pentamethyl)cyclopentadienyl.

7. The complex according to any of claims 1-5, characterized in that Cp is cyclopentadienyl.

8. The complex according to any of claims 1-7, characterized in that M is zirconium.

9. The complex according to any of claims 1-7, characterized in that M is hafnium.

10. A polymerization catalyst system of phosphates, characterized in that it comprises: A) a complex having the formula (PI)(Cp)ML2, wherein: I) PI is a phosphinimine ligand defined by the formula: R1' R1— P—NR1 wherein N is a nitrogen atom; P is a phosphorus atom; each R1 is unsubstituted or substituted adamantyl; and R1' is selected from the group consisting of unsubstituted adamantyl, substituted adamantyl and hydrocarbyl C ia C g; II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered carbon ring having a delocalized bond within the ring and bonded to M, the ring of which is unsubstituted or may be further substituted; III) each L is an activatable ligand; and IV) M is zirconium or hafnium; and B) an activator.

11. The olefin polymerization catalyst system according to claim 10, characterized in that the activator is selected from the group consisting of an aluminoxane; an organoaluminum compound; an ionic activator; and mixtures thereof.

12. The olefin polymerization catalyst system according to claim 10, characterized in that R1' is unsubstituted adamantyl or substituted adamantyl. 110 13. The olefin polymerization catalyst system according to claim 10, characterized in that R1' is unsubstituted adamantyl.

14. The olefin polymerization catalyst system according to claim 13, characterized in that each R1 is unsubstituted adamantyl.

15. The olefin polymerization catalyst system according to claim 14, characterized in that R1' and each R1 is 1-adamantile.

16. The olefin polymerization catalyst system according to any of claims 10-15, characterized in that Cp is (pentamethyl)cyclopentadienyl.

17. The olefin polymerization catalyst system according to any of claims 10-15, characterized in that Cp is cyclopentadienyl.

18. The olefin polymerization catalyst system according to any of claims 10-17, characterized in that M is zirconium.

19. The olefin polymerization catalyst system according to any of claims 10-17, characterized in that M is hafnium.

20. A process for the polymerization of olefins, characterized in that it comprises contacting one or more ethylene and C3 to C10 alpha olefins with the olefin polymerization catalyst system in accordance with any one of claims 10-19 under polymerization conditions.

21. The process according to claim 20, characterized in that one or more of the ethylene and C3 to C10 alpha olefins consist of a) ethylene; and b) one or more olefins selected from the group consisting of 1-butene; 1-hexene; and 1-octene.

22. A process for the (co)polymerization of ethylene, characterized in that it comprises: A) preparing a first polymer solution by polymerizing ethylene, optionally with one or more C3 to C10 alpha olefins, in a solvent in a first polymerization reactor at a temperature of 80 to 200°C and a pressure of 6894.76 kPa to 55,158.07 psi (1000 to 8000 psi) in the presence of (i) the complex according to claim 1; and (ii) an activator consisting essentially of an aluminoxane and an ionic activator; and B) passing the first polymer solution to a second polymerization reactor and (co)polymerizing ethylene, optionally with one or more C3-C10 alpha olefins, in the presence of a Ziegler-Natta catalyst.

23. A process for the (co)polymerization of ethylene, characterized in that it comprises: A) preparing a first polymer solution by polymerizing ethylene, optionally with one or more C3-C10 alpha olefins, in a solvent in a first polymerization reactor at a temperature of 80 to 200°C and a pressure of 6894.76 kPa to 55,158.07 psi (1000 to 8000 psi) in the presence of (i) the complex according to claim 1; and (ii) an activator consisting essentially of an organoaluminum compound and an ionic activator; and B) passing the first polymer solution to a second polymerization reactor and (co)polymerizing ethylene, optionally with one or more C3-C10 alpha olefins, in the presence of a Ziegler-Natta catalyst.