TITANIUM CYCLOPENTADIENYL / ADAMANTYLPHOSPHENIMIN COMPLEXES

Abstract

This description provides titanium complexes containing 1) a cyclopentadienyl ligand; 2) an adamantyl-phosphinimine ligand; and 3) at least one activatable 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) and enable the production of high molecular weight copolymers (Mw greater than 25,000) with high productivity under solution polymerization conditions.

Description

TITANIUM CYCLOPENTADIENYL / ADAMANTYLPHOSPHENIMIN COMPLEXES Field of Invention The present description relates to novel titanium complexes having a cyclopentadienyl-type ligand and a phosphinimine ligand bearing an adamantil moiety (substituted or unsubstituted) and definite polymerization catalyst systems employing these complexes. Background of the Invention Titanium complexes having a cyclopentadienyl ligand and a phosphinimine ligand, and the use of the complexes as catalysts for the polymerization of definites, are described in U.S. Patent No. 6,063,879 (Stephan et al., of NOVA Chemicals International SA). Summary of the Invention In one embodiment, the present description provides a complex having the formula (PI) (Cp) TiL2, 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 or substituted adamantyl; and R1' is selected from the group consisting of Ref. 337995 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 Ti, whose ring is either unsubstituted or may be further substituted. III) each L is an activatable ligand; and IV) Ti is titanium. In another embodiment, the present description provides a polymerization catalyst system comprising: A) a complex having the formula (PI) (Cp)TiL2, where: I) PI is a phosphinemine ligand defined by the formula: R1' 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 C ia C 6 II) Cp is a cyclopentadienyl-type ligand that / £07 ίΩ / 77Ω7 / Β / YILI comprises a 5-membered carbon ring having a delocalized bond within the ring and is attached to M, whose ring is unsubstituted or may be further substituted; III) each L is an activatable ligand; and IV) Ti is titanium, and B) an activator. In another embodiment, the present description provides a process for the polymerization of olefins comprising contacting one or more C2 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)TiL2, 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 / £07 ίΩ / 77Ω7 / Β / YΙΛΙ Ci to C6; ίη / ZZΖΠZ / E / YΙΛΙ 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) Ti is titanium, and B) an activator. In one embodiment, the present description provides a complex that has the formula: where each L is an activatable ligand. In one embodiment, the present description provides a complex that has the formula: where each L is an activatable ligand. In one embodiment, the present description provides a complex that has the formula: / £07 Ω / 77Ω7 / B / YILI where each L is an activatable ligand. In another embodiment, the present description provides a polymerization catalyst system comprising: where each L is an activatable ligand; and B) an activator. In another embodiment, the present description provides a polymerization catalyst system comprising: A) a complex that has the formula: ΖΓ07 ίη / 77Ω7 / Β / ΥΙΛΙ where each L is an activatable ligand; and B) an activator. In another embodiment, the present description provides an olefin polymerization catalyst system comprising: A) a complex that has the formula: where each L is an activatable ligand; 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 activatable ligand; 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 C3a Ci0 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 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) complex that has the formula: / £07 ίη / 77Π7 / E / YΙΛΙ where each L is an active ligand; 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., triphyll borate, [Ph3C][B(CeF5)4]). Brief Description of the Figures Figure 1 shows the dependence of the molecular weight of polyethylene on the BHEB / A1 ratio for one modality of the present description and for a comparative example. Figure 2 shows the polymerization activity of a complex of the present description, Cp (1-AdaPN)TÍCI2 and for a comparative complex, Cp(tBuaPN) T1CI2 . Detailed Description of the Invention As used herein, the term unsubstituted means that the hydrogen radicals are attached to the molecular group to which the term unsubstituted refers. The term substituted means that the group to which this term refers has one or more substituents that have replaced one or more hydrogen radicals at any position within the group; non-limiting examples of substituents 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 or germanyl group, hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, phenyl groups, naphthyl groups, C1-C10 alkyl groups, C2-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 bond to carbon. The term containing heteroatoms or a hydrocarbyl group containing heteroatoms means that one or more atoms other than carbon may be present in the hydrocarbyl group. Some non-limiting examples of non-carbon atoms that may be present in a heteroatom containing a hydrocarbyl group 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 fractions, oxide fractions, 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 herein, 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 alkylaryl group is an alkyl group with an aryl group attached to it; non-limiting examples include benzyl, phenethyl, and tolylmethyl. An arylalkyl is an aryl group with 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 of the same name; 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' R1— P=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 C6 hydrocarbyl. For reference, the numbering of a framework of adamantyl carbon atoms is provided below, whether in a substituted or unsubstituted adamantyl moiety, as mentioned in this description: / £07 ίΠ / 77Ω7 / Β / YILI 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 ίΠ / ZΖΖηZΖ / E / YΥΙΛΙ 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 form, each R1 is a substituted adamantite. 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 substituent methyl group at position 3 and position 5. In one embodiment, R1' is a substituted 1-adamantyl having a substituent methyl group 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 hydrocarbyl radicals Ci-io (the hydrocarbyl radical may be unsubstituted or further substituted, for example, by a halide group and / or a hydrocarbyl; for example, a suitable substituted hydrocarbyl radical Ci-io is a pentafluorobenzyl group such as CH2CgF5); an alkyl radical Ci-4; an alkoxy radical Ci-s; an aryl or aryloxy radical Cg-io; an amido radical that is either unsubstituted or substituted with up to two alkyl radicals. ZΓ07 ίη / 77Ω7 / Β / YΙΛΙ Ci-g; an unsubstituted phosphide radical or one substituted by up to two alkyl radicals; Ci-g silyl radicals of formula -Si(R)3 where each R is independently selected from the group consisting of hydrogen, an alkyl or alkoxy radical; Ci-g and aryl or aryloxy radicals; Cg-io silyloxy radicals and germanyl radicals of formula Ge-(R)3 where R is as directly defined above. Cyclopentadienyl-type ligands may also contain heterocyclic moieties 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 (CHgCgFg) . In one embodiment, the cyclopentadienyl-type ligand is (pentafluorobenzyl)cyclopentadienyl, CpíCHgCeFs). In one embodiment, the cyclopentadienyl ligand is tetramethyl(3,5-tert-butylphenyl)cyclopentadienyl, CpMe4(-3,5t-Bu2-C6H3). In one embodiment of the description, the cyclopentadienyl 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 olefin polymerization. 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 abstracts from the metal center M (e.g., a halide can be converted into an alkyl group). Without adhering 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 Cg-io, each of which the hydrocarbyl, alkoxy, and aryl oxide radicals may be substituted or unsubstituted by a halogen atom; an alkyl radical Ci-a; an alkoxy radical Ci-g; an aryl or aryloxy radical Cg-io; an amido radical that is unsubstituted or substituted with up to two alkyl radicals Ci-s; and a phosphide radical that is unsubstituted or substituted with up to two alkyl radicals Ci-g. Two L-activatable ligands can also bond together to form, for example, a substituted or unsubstituted diene ligand (e.g., 1,3-diene); or a group containing a delocalized heteroatom such as an acetate group. The number of activatable ligands depends on the valence of the metal and the valence of the activatable ligand. In some embodiments, the preferred phosphinimine catalysts are based on group 4 metals in their highest oxidation state (i.e., 4+). Particularly suitable active ligands are monoanionic ligands such as a halide (e.g., chloride) or a hydrocartyl (e.g., methyl, denyl). In some cases, the phosphinimine catalyst metal may not be in its highest oxidation state. For example, a titanium(III) component would contain only one active ligand. In one version of the description, the active ligand L is methyl. In one version of the description, the active ligand L is dencil (Bn to adverbial). In one version of the description, the activating ligand L is chloride. ίη / ZZΖΠZ / E / YΙΛΙ 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 R^AÚO (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 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 group 4 transition metal Alh are 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 Ci-io 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) p where R3 and R3 are each independently hydrocarbyl groups Ci to C2o,' X is a halide; m + 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 C5-7 cyclic aromatic cation or a triphenyl methyl 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 C1-4 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 C1-4 alkyl radical; (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-g alkyl radicals, a phenyl radical that is not 7GO7 ίη / 77P7 / E / YILI is substituted or is substituted with up to three C1-4 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 wherein 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 (e.g., PhR82NH+, which is substituted by two R8 radicals such as, for example, two Ch-4 alkyl radicals). Examples of compounds capable of ionizing the single-site catalyst include the following compounds: tetra(phenyl)boro di triethylamonium, tetra(phenyl)boro di tripropylamonium, tri(n-butyl)ammonio tetra(phenyl)boro, tetra(ptolyl)boro di trimethylamonium, tetra(o-tolyl)boro di trimetilamonio, tetra(pentafluorophenyl)boro di tripropylamonium, tetra(o,p-methylphenyl)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, tetra(phenyl)boro de N,N-2,4,6-pentametianilinio, tetra(pentafluorophenyl)boro de di-(isopropyl)ammonio, tetra(phenyl)boro de dicyclohexilamonio, tetra(phenyl)boro de triphenylphosphonio, tetra(phenyl)boro di tri(methylphenyl)phosphonio, tetra(phenyl)boro de tri(methylphenyl)phosphonio,tetrakispentafluorophenyl borate of tropyllum, tetrakispentafluorophenyl borate of triphenylmethyl, tetrakispentafluorophenyl borate of benzene(diazonium), phenyltris-pentafluorophenyl borate of tropyllum, phenyltrispentafluorophenyl borate of triphenylmethyl, phenyltrispentafluorophenyl borate of benzene(diazonium), tetrakis(2,3,5,6-tetrafluorophenyl)borate of tropyllum, 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 benzene(diazonium), tetrakis(1,2,2-trifluoroethenyl)borate of tropyllum, tetrakis(1,2,2-trifluoroethenyl)borate of tropyllum, tetrakis(1,2,2-trifluoroethenyl)borate of benzene(diazonium), tetrakis(2,3,4,5-tetrafluorophenyl)borate of tropyl, 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-dimethylaniliniotetrakispentafluorophenyl borate ([Me2NHPh][B(CgF5)4]); triphenylmethyl tetrakispentafluorophenyl borate ([PhaC][B(CgFs)4]); and trispentafluorophenyl boron and MAO (methylaluminoxane) and MMIO (modified methylaluminoxane). Ionic activating compounds can be used in amounts that provide a group 4 transition metal to boron molar ratio 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 used 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 di-tert-butyl-4'-hydroxyphenyl octadecyl-3(3',5r-propionate). Catalyst 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 catalyst 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 the polyolefin monomer and catalyst composition are added, and which contains a liquid reaction medium for dissolving or suspending 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 catalyst 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 polyolefin monomer and the catalyst 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 a polymerization process of olefins comprising contacting one or more ethylene and C3 to C10 alpha olefins with the olefin polymerization catalyst system described herein under polymerization conditions. ίη / ZZΖΠZ / E / YΙΛΙ One embodiment of the description is a polymerization process of olefins comprising contacting one or more ethylene and C3a 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 1894.76 kPa (1 to 1000 psi), such as 344.74 kPa to 2757.9 kPa (50 to 400 psi), for example, from 689.48 kPa 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 passing a stream containing one or more olefin monomers continuously 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 a suspended condition.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 employed as poison-removing agents to increase catalyst activity. Examples of sequestering 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 functioning of the catalyst composition in the formation of 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 moles of hydrogen per mole of total monomer feed. Olefin 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 from 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. Olefin polymers 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, the 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, vinyltrialkyl silanes, and the like, can also be polymerized according to the description. Specific 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 where 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 be in the range from 15 to 45 atmospheres (approximately 220 to 660 psi or approximately 1500 to approximately). 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 vessel reactor that has an internal agitator (e.g., an impeller) and at least one settling column. The catalyst, monomers, and diluents are fed to the reactor as liquids or slurries. The slurry circulates through the reactor, and the jacket is used to control the reactor temperature.Through a series of discharge valves, the slurry enters a sedimentation column, where the pressure is then 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 (Cg-12 aliphatic solvent, 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 the Patent. American Common Assignment No. 6,024,483. In some embodiments, the preferred pressures are from approximately 3447.38 kPa to 55158.07 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, from approximately 1500 psi to 3000 psi (approximately 10,000 to 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 and one catalyst is a Ziegler-Natta (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 are used In series CSTRs, 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 CSTR tubular reactor is at least 100 liters; for example, from 300 to 2,000 liters). 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 C3-e alkyl groups. Illustrative, but not limited to, examples of such alpha-olefins are one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene, as well as mixtures thereof. In some embodiments, 1-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 Ganada Inc.). The residence time in each reactor will depend on the reactor design and capacity. Generally, reactors can be operated under conditions that achieve thorough 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-d8, toluene-d8) were purchased from Aldrich and stored over activated 4α molecular sieves. The deuterated solvent (chloroform-d, dichloromethane-d2, toluene-d8) was purchased from Cambridge Isotope and stored over activated 4α molecular sieves. NMR spectra were recorded on a Bruker 400 MHz spectrometer (1H: 400.1 MHz, 19F: 376 MHz, 31P: 162 MHz). 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 to 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, with 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 using narrow-distribution polystyrene standards.The molecular weights of polystyrene were converted to molecular weights of polyethylene using the Mark-Houwink equation, as described in the ASTM D6474 standard test method. Comonomer content by Fourier transform infrared spectroscopy (FTIR): The amount (mole percent (or weight percent) 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) 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 Lithium aluminum hydride (7.25 g; 191 mmol) was added as a solid to a solution of bis(1-adamantyl)phosphinic chloride (27.0 g; 76 mmol) in THF (200 mL) at -40°C as a solid in small portions over 1.5 hours in a glovebox. 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%). RMNXH (CD2Cl2, δ, ppm): 2.78 (d, JPH = 208 Hz, H), 1.91 (m, 18H), 1.72 (s, 12H). NMR31Ρ{ΧΗ} (CD2C12, δ, ppm): 17.70 (s). Preparation of 1-adamantylacetate 7ΓΟ7 ίη / ΖΖΠΖ / Ε / ΥΙΛΙ At room temperature, silver trifluoroethane sulfonate (0.040 g, 0.16 mmol) was added to a mixture of 1-adamantanol (2.35 g, 15.4 mmol) and acetic anhydride (2.2 mL, 23.3 mmol). 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 MgS₂Cu₂. The organic layer was filtered, and the volatiles were removed to give a clear, colorless liquid (0.91 g, 91%). RMNXH (CD2CI2, δ, ppm): 2.14 (br, 3H), 2.09 (s, 6H), 1.92 (s, 3H), 1.66 (s, 6H). Preparation of tri(1-adamantyl)phosphine / £07 ίΩ / 77Ω7 / Β / ΥΙΛΙ At room temperature, trimethylsilyl trifluoromethane sulfonate (8.5 mL, 46.5 mmol) was added to a solution of bis(1-adamantyl)phosphine (11.75 g, 38.9 mmol) and 1-adamantyl acetate (8.30 g, 46.5 mmol) in dichloromethane (100 mL). The reaction was stirred at room temperature for 24 hours. Trimethylamine (26 mL, 187 mmol) 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 vacuum dried to give pure tri(1-adamantyl)phosphine (15.79 g, 93%). NMR (CD2C12, δ, ppm): 2.21 (br, 18H), 1.92 (s, 9H), 1.74 (quartet, 18H). 31P{1H} NMR (CD2Cl2, δ, ppm): 59.23 (s). Preparation of N-trimethylsilyl Tri(ladamantyl)phosphinemine P=N-TMS Trimethylsilylazide (3 mL) was added to a solution of tri(1-adamantyl)phosphine (10.0 g, 23.0 mmol) in toluene (250 mL) at room temperature. The reaction was heated to 90°C, and then 9 mL of trimethylsilylazide were added for a total of 12 mL of trimethylsilylazide (12 mL, 90.4 mmol). 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%). RMNXH (toluene-dg, δ, ppm): 2.31 (br, 18H), 1.92 (s, 9H), 1.74 (quartet, 18H), 0.47 (s, 9H). 31P{1H) NMR (toluene-d8, δ, ppm): 19.3 (s). Preparation of tri(1-adamantyl)phosphiniminate cyclopentadienyl titanium dichloride, Cp (Ad3PN) T1C12(1-Ad = l-adamantyl; Cp = cyclopentadienyl) To a solution of cyclopentadienyltitanium trichloride (0.204 g, 0.93 mmol) in toluene (25 mi) was added a suspension of N-trimethylsilyl tri(1-adamantyl)phosphinimine (0.487 g, 0.93 mmol) in toluene (15 mi) at room temperature. The reaction was heated to 90°C overnight. The reaction was cooled to room temperature and the volatiles were removed in vacuo. A yellow solid (0.496 g, 84%) was collected. NMR1H (toluene-dg, δ, ppm): 6.48(s,10). 5Η), 2.47 (br, 18H), 2.09 (s, 9H), 1.80 (quartet, 18H). NMR ^PpH) (toluene-dg, δ, ppm) : 32.73(s) . Preparation of 1-pentafluorophenyl-2propylcyclopentadienyl tri (1-adamantyl)phosphiniminate titanium dichloride, (l-C6F5-2-n-C3H7-Cp) ( (l~Ad)3PN) TiCl2 7ΓΟ7 ίη / 77Π7 / Ε / ΥΙΛΙ In a nitrogen-filled glove box, a solution of 1-(CgF5)-2-n-C3H7-CpTiCl3 in toluene (4 mL, 0.153 M, 0.260 g, 0.611 mmol) was added to a 20 mL vial. The vial was cooled to 0°C, and a suspension of (1-Ad)3PNSiMe3 (0.320 g, 0.611 mmol) in 4 mL of toluene was added. While stirring at 200 rpm, the glass vial was heated to 100°C overnight. After approximately 12 hours, the reaction was cooled to room temperature, and the volatiles were removed under dynamic vacuum, resulting in a light green solid (0.598 g) that was recrystallized from a mixture of toluene and cyclohexane, yielding 0.507 g (81.5% yield) of pure product. 4H NMR (CDC13, δ, ppm): 6.86 (triplet, 1H), 6.38 (br, 1H), 6.14 (triplet, 1H) 2.48 (br, 18H), 2.11 (br, 8H), 2.03 (br, 3H), 1.77 (br, 22H) . NMR31P{1H) (CDC13, δ, ppm) : δ 32.79 (s). NMR19F (CDCI3, δ, ppm): -135.37 (br, 2F), -155.90 (triplet, 1F), -162.71 (multiplet, 2F). Preparation of titanium pentafluorobenzylcyclopentadienyltri(1-adamantyl)phosphiniminate dichloride, (C6F5CH2-Cp) ((1-Ad)3PN)TiCl2 In a nitrogen-filled glove box, a solution of (C6F5CH2)CpTiCl3 in toluene (4 mL, 0.153 M, 0.243 g, 0.382 mmol) was added to a 20 mL vial. The vial was cooled to 0°C, and a suspension of (1-Ad)3PNSiMe3 (0.320 g, 0.611 mmol) in 4 mL of toluene was added. While stirring at 200 rpm, the glass vial was heated to 100°C overnight. After approximately 12 hours, the reaction was cooled to room temperature, and the volatiles were removed under dynamic vacuum, resulting in 0.521 g of a yellow solid, which was recrystallized from a mixture of toluene and cyclohexane. Yield (0.504 g, 99.5%). ΗNMR4 (CDC13, δ, ppm): 6.47 (t, 2H), 6.29 (t, 2H), 4.05 (s, 2H), 2.48 (s, 18H), 2.12 (s, 9H), 1.81 (m, 18H). ^PpH} NMR (CDC13, δ, ppm): δ 32.73. 19F NMR (CDCI3, δ, ppm): -143.15 (dd, 2F), -157.29 (t, 1F), -162.47 (m, 2F) Preparation of p eJΩΛJΠϊUϊjLJLL·oJL·zJL·^^tri (1 adamanti 1) phosphiniminate titanium dichloride, Cp* ( (1-Ad)3PN ) TiC12 / £07 ίΩ / 77Ω7 / Ε / ΥΙΛΙ In a nitrogen-filled glove box, Cp*C13 (500 mg, 1.73 mmol) and (1-Ad)3PNS iMes (0.905 g, 1.73 mmol) were added to a 100 mL Schlenk vessel, followed by o-xylene (30 mL). The Schlenk vessel was heated to 130°C overnight while open to a nitrogen bubbler. The volatiles were removed at 60°C under dynamic vacuum, leaving an orange solid, which was recrystallized from a toluene-pentane mixture. Yield (1.116 g, 89.8%) RMNXH (CDCI3, δ, ppm): 2.43 (br, 18H,) 2.17 (s, 15H), 2.08 (br, 9H), 1.74 (br, 18H). ^PpH} (CDC13, δ, ppm): 32.2 (s). Preparation of bis(3,5-dimethyl-l-adamantyl)phosphine, (3,5Me2-1-Ad)2PH) 1,3-Dimethyladamantane (10 g, 60.86 mmol) and AICI3 (9.5 g, 71 mmol) were weighed into a 150 mL Schlenk flask with a large stirring rod. PC13 (40 mL) was added to the flask. The mixture was stirred and heated to 90°C overnight. An orange-colored suspension was produced. Excess PC13 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 (O) 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. LiAlH4 (3.5 g, 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 × 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). 1H NMR (toluene-dg, δ, ppm): 2.92 (d, J = 201.64 Hz, 1H), 1.97-1.89 (m, 2H), 1.871.68 (m, 4H), 1.65-1.55 (m, 4H), 1.55-1.44 (m, 4H), 1.32-1.15 (m, 8H), 1.01 (s, 4H), 0.78 (s, 12H). NMR31P (toluene-dg, δ, ppm): 14.70 (s). Preparation of (1-adamantyl)bis(3,5-dimethyl-adamantyl)phosphine, (1-Ad) (3,ó-Meg-l-Ad) 2P Bis(3,5-Dimethyl-l-adamantyl)phosphine (5.0 g, 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 not soluble in EtOH) was dried in vacuo (3.50 g, 51% yield). 3H NMR (toluene-dg, δ, 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-dg, δ, ppm): 55.9 (s). Preparation of (1-adamantyl) bis (3,5-dimethyl-ladamantyl) (N-trimethylsilyl) phosphinimine,(1-Ad)(3,5-Me2~lAd)2) P=NSiMe3 Weighed (1-adamantyl)bis (3,5-Me2-l-adamantyl)gphosphine (3.50 g, 7.10 mmol) in a 250 ml Schlenk test. If added tolueno (~70 ml) and trimethylsilyl azide (3.0 ml, 21.3 mmol) . The mixture was heated to 110°C for 6 hours and the contents were boiled until ready to give a night foam (1.24 g). RMN1H (toluene-dg, δ, ppm) : 6.50 (s, 5H) , 2.74-2.11 (m, 16H), 2.01-1.82 (m, 6H) , 1.80-1.48 (m, 7H), 1.48-1.06 (m, 12H) , 0.85 (s, 12H). RMN31P (toluene-dg, δ, ppm): 22.9 (s). N-trimethylsilyl preparation of (1adamantyl)butylfosphinimine ΖΓ07 ίη / 77Ω7 / Β / ΥΙΛΙ To a solution of di(1-adamantyl)butylphosphine (1.135 g, 3.17 mmol) in toluene (30 mL) at room temperature, trimethylsilylazide (1.0 mL) was added. The reaction was heated to 60°C, and then an additional 4 mL of trimethylsilylazide was added for a total of 5 mL of trimethylsilylazide (5 mL, 38 mmol). The reaction was heated under reflux at 110°C overnight. The reaction was allowed to cool to room temperature, and the volatiles were removed under vacuum to give a peach-colored solid (1.34 g, 95%). NMR ^(CDClg, δ, ppm): 1.97 (s, 6H, 1-Ad), 1.93 (s (wide), 12H 1-Ad), 1.71 (s, 12H, 1-Ad), 1.40 (s (wide), 6H, -CH2CH2CH2CH3) , 0.93 (s (wide), 3H, CH2CH2CH2CH3), 0.01 (s, 9H, (Si(CH3)3) NMR ^PpH} (CDCI3, δ, ppm): 19.3 (s). Preparation of cyclopentadienyl di(ladamantyl)butylphosphiniminate titanium dichloride, Cp ((1-Ad) 2BUPN)TICI2 (1Ad = 1-adamantyl; Cp = cyclopentadienyl) / £07 ίΩ / 77Ω7 / Β / ΥΙΛΙ A suspension of trimethylsilyl di(1-adamantyl)butylphosphine N (1.34 g, 3.01 mmol) in toluene (15 ml) was added to a solution of cyclopentadienyltitanium trichloride (0.72 g, 3.28 mmol) in toluene (25 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. A yellow solid (1.6 g, 88%) was collected. NMRΣΗ (toluene-dg, δ, ppm): 6.48 (s, 5H, Cp-H), 2.09 (m (width), 12H, 1-Ad), 1.88 (s (width), 8H, 1-Ad and -CH2CH2CH2CH3), 1.64 (m, 12H, 1-Ad), 1.43 (m (width), 4H, -CH2CH2CH2CH3), 1.01 (t, J = 6 Hz, 3H, -CH2CH2CH2CH3). NMR (toluene-d8, δ, ppm) : 28.7 (s). Continuous Solution Polymerization. Continuous polymerizations were carried out 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 less 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(l-AdaPN)TICl2) and (Ph3C)[B(CeFs)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 unit.MMAO-7 is a commercially available methylaluminoxane that is reported to contain 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: kP= (Q / ( 100-Q) ) (1 / ([M])) (1 / HUT) where Q is the ethylene conversion (%) (measured with 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, ground, and then analyzed by FTIR (for short chain branching frequency) and GPC-RI (for molecular weight and distribution). Polymerization results In this example (Example A), comparative and novel catalysts were used. The comparative catalyst is Cp(t-BU3PN)TiCl2, which is known to be an excellent catalyst for solution polymerization. The novel catalyst, Cp(1-AdsPN)TiCl2, produces a polymer molecular weight (MW) independent of the BHEB / A1 ratio, resulting in consistent products. In contrast, the molecular weight of the polymers produced by the Cp(tBusPN)TiCl2 catalyst decreases with increasing BHEB / A1 ratio. The molecular weight of the polymer versus the BHEB / A1 ratio are tabulated in Table 1 and represented in Figure 1. ίη / ZZΖΠZ / E / YΙΛΙ TABLE 1 Molecular weight versus BHEB / A1 ratio at 160°C; Weight ratio of 1-octene / ethylene = 0.5 Molar ratio of BHEB / AI 0 0.1 0.2 0.3 0.5 0.7 Molecular weight of polyethylene when using Cp(tBu3PN)TiCl2 77948 73098 73098 71219 66244 64324 Molecular weight of polyethylene when using Cp(1-Ad3PN)TiCl2 68060 62951 66904 63920 64820 62848 The activity data for the catalyst Cp(l-Ad3PN)TiCl2 and a comparative catalyst Cp(tBu3PN)T1CI2 at 130°C, 140°C, and 160°C without the addition of BHEB are tabulated in Table 2 and represented in Figure 2. When the BHEB / A1 molar ratio was zero, i.e., when BHEB was not present to remove trimethylaluminum from MAC, the catalyst Cp(lAd3PN)TiCl2 was more active than Cp(tBu3PN)TiCl2, indicating that the catalyst is less sensitive to trimethylaluminum. TABLE 2 Activity (¿p) versus reactor temperature, at a 1-octene / ethylene ratio = 0.5; Al / Ti ratio = 80; and a BHEB / A1 ratio = 0 Temperature (°C) 130 140 160 Activity (kp) of CpOBuaPNjTiCk 8700 5472 2100 Activity (kp) of Cp(1Ad3RN)T¡CI2 16210 14300 7800 Tables 3, 4, and 5 (Example B) present additional polymerization results using more titanium-based catalyst complex derivatives having a cyclopentadienthyl-type ligand and a phosphinimine ligand bearing an adamantyl moiety (including substituted and unsubstituted adamantyl moiety moiety) together with comparative results obtained using Cp(tBu3PN) TIC12. The polymers were fabricated using a continuous solution polymerization process in a CPU unit as previously described; However, in addition to using MAO as a cocatalyst (or eliminator), other organoaluminum compounds were also explored, such as triethylaluminum (TEAL), tributylaluminum (TiBAl), tri-n-octylaluminum (TnOAl), and diethylaluminum ethoxide (Et2A10Et), as shown in Tables 3, 4, and 5. In these examples, the use of varying levels of a hindered phenol (BHEB) was again explored. TABLE 3 Polymerization results with Cp((1-Ad')2(1~ Ad)PN)TiCl2 catalyst versus Cp(tBu3PN)TiCl2 Example, Temp Complex. (°C) Al / Ti scrubber (mol / mol) BHEB / AI (mol / mol) C8 / C2 (P / P) B1, CpCBusPNjTiCb (Comparative) 140 MAC 80 0.3 0.5 B2, Cp((1-Adj2(1-Ad)PN)T¡CI2 140 MAC 80 0.3 0 B3, Cp((1-Adj2(1-Ad)PN)TICI2 140 MAC 80 0.3 0.15 B4, Cp((1-Adj2(1-Ad)PN)T¡CI2 140 MAC 80 0.3 0.30 B5, Cp((1-Adj2(1-Ad)PN)T¡CI2 140 MAC 80 0.3 0.50 B6, Cp((1-Adj2(1-Ad)PN)TICI2 140 MAC 80 0 0.50 B7, Cp((1-Adj2(1-Ad)PN)TíCI2 140 MAC 10 0 0.50 B8, CpCBuaPNjTiCb (Comparative) 190 MAC 80 0.3 0.5 B9, Cp((1-Adj2(1-Ad)PN)T¡CI2 190 MAO 80 0.3 0 B10, Cp((1-Adj2(1-Ad)PN)T¡CI2 190 MAO 80 0.3 0.15 B11, Cp((1-Adj2(1-Ad))(1-Adj2) MAO 80 0.3 0.30 B12, Cp((1-Adj2(1-Ad)PN)T¡CI2 190 MAO 80 0.3 0.50 B13, Cp((1-Adj2(1-Ad)PN)T¡CI2 190 MAO 80 0 B14.50 Cp((1-Adj2(1-Ad)PN)T¡CI2 190 MAO 10 0 0.50 B15, Cp((1-Adj2(1-Ad)PN)T¡CI2 190 TEAL 10 0 0.50 B16, Cp((1-Adj2(1-Ad)A 10 0 0.50 B17, Cp((1-Adj2(1-Ad)PN)T¡CI2 190 Et2AIOEt 10 0 0.50 B18, Cp((1-Adj2(1-Ad)PN)T¡CI2 190 TiBAI 10 0 0.50 / £07 ίΩ / 77Ω7 / Β / ΥΙΛΙ 1-Ad = 1-adamantyl; 1-Ad' =3.5-Me2_l-Ad; molar ratio of [Ph3C][B(C6F5)4] / Ti = 1.2; BHEB = 2,6-di-terc-butyl-4-ethylphenol. TABLE 3 ~ CONTINUED Polymerization results with Cp ( (1-Ad')2(1~ Ad)PN)TiCl2 catalyst against Cp(tBu3PN)TiCl2 Example, Complex Activity (kP) SCB / 1000C Mw PD (Mw / Mn) B1, Ορ(ιΒυ3ΡΝ)ΤίΟΙ2 (Comparative) 18.682 8.3 113.157 1.62 B2, Cp((1-Adj2(1-Ad)PN)TiCI2 40.006 <0.5 222.442 1.64 B3, Cp((1-Adj2(1-Ad)PN)TiCI2 20.491 2.6 150.482 1.78 B4, Cp((1-Adj2(1-Ad)PN)TICI2 15.832 4.5 135.900 1.71 B5, Cp((1-Adj2(1-Ad)PN)T¡CI2 13.050 7.4 112.503 1.74 B6, Cp((1-Adj2(1-Ad)PN)TÍCI2 8,922 7.3 115,279 1.8 B7, Cp((1-Adj2(1-Ad)PN)TÍCI2 9,357 7.4 110,446 1.62 B8, Ορ(ιΒυ3ΡΝ)ΤίΟΙ2 (Comparativo) 2,078 10.1 39,147 1.86 B9, Cp((1-Adj2(1-Ad)PN)T¡CI2 3,560 <0.5 74,290 1.74 B10, Cp((1-Adj2(1-Ad)PN)TÍCI2 3,402 2.7 53,760 1.8 B11, Cp((1-Adj2(1-Ad)PN)TÍCI2 3,360 5.5 44,499 1.93 B12, Cp((1-Adj2(1-Ad)PN)T¡CI2 3,230 8.2 38,827 1.74 B13, Cp((1-Adj2(1-Ad)PN)T¡CI2 1,788 8.6 41,592 2.02 B14, Cp((1 -Adj2(1 -Ad)PN)T¡CI2 742 9.5 32,404 3.06 B15, Cp((1-Adj2(1-Ad)PN)TÍCI2 950 9.8 31,978 2.94 B16, Cp((1-Adj2(1-Ad)PN)TÍCI2 947 9.8 30,757 3.03 B17, Cp((1-Adj2(1-Ad)PN)T¡CI2 1,944 7.7 41,287 1.71 B18, Cp((1-Adj2(1-Ad)PN)T¡CI2 1,103 8.7 35,048 2.81 TABLA 4 Resultados de polimerización con otros catalizadores de adamantilfosfiniminato de titanio a 140°C Example, Activator Complex BHEB / AI (mol / mol) C8 / C2 (w / w) Activity (kP) SCB / 1000C Mw PD (Mw / Mn) B19, Cp('Bu3PN)TICl2 (Comparative) [Ph3C][B(C6F5)4] 0.3 0.5 18,682 8.3 113,157 1.62 B20, Cp*((1-Ad)3PN)TICl2 [Ph3C][B(C6F5)4] 0.3 0.15 2,124 1.9 239,785 2.66 B21, Cp*((1-Ad)3PN)TICl2 [Ph3C][B(C6F5)4] 0.3 0.30 1,082 2.5 207,708 2.59 B22, Cp*((1-Ad)3PN)TiCI2 [Ph3C][B(C6F5)4] 0.3 0.50 794 3.4 176,612 2.06 B23, Cp*((1-Ad)3PN)TiCI2 [Ph3C][B(C6F5)4] 0 0.30 737 1.8 164,725 1.88 B24, Cp*((1-Ad)3PN)T¡CI2 B(C6F5)3 0.3 0.30 671 1.7 176,371 1.87 B25, (C6F5CH2-Cp)((1Ad)3PN)TICI2 [Ph3C][B(C6F5)4] 0.3 0.15 15,719 3.4 126,060 1.66 ίΠ / ZZΖηZ / E / YΙΛΙ B26, (C6F5CH2-Cp)((1Ad)3PN)T¡CI2 [Ph3C][B(C6F5)4] 0.3 0.30 12,063 6.0 104,964 1.75 B27, (C6F5CH2-Cp)((1Ad)3PN)T¡CI2 [Ph3C][B(C6F5)4] 0.3 0.50 10,247 9.5 89,225 1.77 B28, (C6F5CH2-Cp)((1Ad)3PN)TiCI2 [Ph3C][B(C6F5)4] 0 0.30 1,445 5.9 127,339 1.74 B29, (C6F5CH2-Cp)((1Ad)3PN)T¡CI2 B(C6F5)3 0.3 0.30 1,507 6.0 111,115 1.77 B30, (1-Pr-2-CeF5-Cp)((1- Ad)3PN)T¡CI2 [Ph3C][B(C6F5)4] 0.3 0.30 2,575 7.0 86,738 2.32 B31,(1-Pr-2-C6F5-Cp)((1- Ad)3PN)TiCI2 [Ph3C][B(C6F5)4] 0.3 0.50 1,998 11.1 70,348 2.22 B32, (1-Pr-2-C6F5-Cp)((1- Ad)3PN)TiCI2 [Ph3C][B(C6F5)4] 0 0.30 428 5.9 115,251 2.07 B33, (1-Pr-2-C6F5-Cp)((1- Ad)3PN)T¡CI2 B(C6F5)3 0.3 0.30 723 7.0 71,571 2.02 B34, Cp((1Ad)2(nBu)PN)T¡CI2 [Ph3C][B(C6F5)4] 0.3 0.00 22,224 B35, Cp((1- Ad)2(nBu)PN)T¡CI2 [Ph3C][B(C6F5)4] 0.3 0.15 20,297 B36, Cp((1- Ad)2(nBu)RN)T¡CI2 [Ph3C][B(C6F5)4] 0.3 0.30 16,634 B37, Cp((1- Ad)2(nBu)PN)T¡CI2 [Ph3C][B(C6F5)4] 0.3 0.50 14,046 B39, Cp((1Ad)2(nBu)PN)T¡CI2 B(C6F5)3 0.3 0.30 1,464 6.0 166,210 1.81 1-Ad = 1-adamantile; molar ratio of (PhsC) [B (CgFs)4] / Ti = 1.2; molar ratio of B (CgFs)3 / Ti = 1.2; molar ratio of Al / Ti = 80; BHEB = 2,6-di-tert-butyl-4-ethylphenol; Debugger = MAO. TABLE 5 Polymerization results with other catalysts of Titanium adamantylphosphiniminate at 190°C / £07 ίΠ / 77Ω7 / Β / ΥΙΛΙ Example, C8 / C2 Complex (w / w) Activity (kP) SCB / 1000C Mw PD Mw / Mn B40, Cp('Bu3PN)TiCl2 (Comparative) 0.5 2,078 10.1 39,147 1.86 B41, (1-Pr-2-C6F5-Cp)((1-Ad)3PN)TiCl2 0.00 616 0.8 38,298 3.17 B42, (1-Pr-2-CsF5-Cp)((1-Ad)3PN)TiCl2 0.15 571 3.9 28,882 3.28 B43, (1-Pr-2-C6F5-Cp)((1-Ad)3PN)TiCl2 0.30 529 6.4 24,305 2.62 B44, (1-Pr-2-C6F5-Cp)((1-Ad)3PN)TiCl2 0.50 476 9.7 18,952 3.22 B45, Cp((1-Ad)2(nBu)PN)T¡CI2 0.00 2,425 0.5 65,523 1.75 B46, Cp((1-Ad)2(nBu)PN)TíCI2 0.15 2,241 3.9 53,256 1.79 B47, Cp((1-Ad)2(nBu)PN)TÍCI2 0.30 2,101 6.5 46,501 1.73 B48, Cp((1-Ad)2(nBu)PN)TiCI2 0.50 1,776 10.2 37,091 1.74 1-Ad = 1-adamantyl; Activator = (PhaC) [B(C6F5)4]; Scrubber = MAO; Al / Ti molar ratio = 80; BHEB / A1 molar ratio = 0.3; (Ph3C) [B (CgF5)4] / Ti molar ratio = 1.2; BHEB = 2,6-di-tert-butyl-4-ethylphenol. The data provided in Tables 3-5 show that more titanium-based complexes having a cyclopentadienyl-type ligand and a phosphinimine ligand carrying a substituted or unsubstituted 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 that has the formula (PI) (Cp)TiL2, where: I) PI is a phosphinemine ligand defined by the formula: R1' 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 Ti, whose ring is either unsubstituted or may be further substituted. III) each L is an activatable ligand; and IV) Ti is titanium. Modality B. The complex according to modality A where R1' is unsubstituted adamantyl or substituted adamantyl. 7ΓΟ7 ίη / ΖΖΠΖ / Β / ΥΙΛΙ ίΠ / ΖΖηΖ / Ε / ΥΙΛΙ 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. Mode H. A polymerization catalyst system comprising: A) a complex having the formula (PI) (Cp)TiL2, where: I) PI is a phosphinemine ligand defined by the formula: Rr 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 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) Ti is titanium, and B) an activator. Mode I. The polymerization catalyst system is defined according to mode H, wherein the activator is selected from the group consisting of an aluminoxane; an organoaluminum compound; an ionic activator; and mixtures thereof. Mode J. The polymerization catalyst system you define according to mode H or I, wherein R1' is unsubstituted adamantyl or substituted adamantyl. Mode K. The polymerization catalyst system is defined according to mode H or I, wherein R1' is unsubstituted adamantyl. Mode L. The polymerization catalyst system is defined according to mode H, I, J or K, wherein each R1 is unsubstituted adamantyl. Mode M. The polymerization catalyst system is defined according to mode H or I, wherein R1' and each R1 is 1-adamantile. Modality N. The polymerization catalyst system / £07 ίΩ / 77Ω7 / B / YILI of you define according to modality H, I, J, K, L or M, where Cp is (pentamethyl)cyclopentadienyl. Mode 0. The olefin polymerization catalyst system according to mode H, I, J, K, Lo M, wherein Cp is cyclopentadienyl. Mode P. 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 Modes H, I, J, K, L, M, N or O under polymerization conditions. Mode Q. The process according to mode P wherein one or more of ethylene and C3a 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. Modality R. A process for the (co)polymerization of ethylene comprising: A) preparing a first polymer solution by polymerizing ethylene, optionally with one or more C3a C10 alpha olefins, in a solvent in a first polymerization reactor at a temperature of 80 to 200°C and a pressure from 6894.76 kPa to 55,158.07 kPa (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 alpha C3-C10 polymers, in the presence of a Ziegler Naphtha catalyst. INDUSTRIAL APPLICABILITY Titanium 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 definite linkage. 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)TiL2, 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 C6 hydrocarbyl; II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered carbon ring having a delocalized bond within the ring and bonded to Ti, the ring of which is unsubstituted or may be further substituted; III) each L is an active ligand; and IV) Ti is titanium.

2. The complex according to claim 1, characterized in that R1' is unsubstituted adamantyl or / £07 ίΩ / 77Ω7 / Β / YΙΛΙ 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. An olefin polymerization catalyst system, characterized in that it comprises: A) a complex having the formula (PI) (CpjTiLg, wherein: I) PI is a phosphinimine ligand defined by the formula: R1' R1— P=N — R1 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 C6 hydrocarbyl; 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) Ti is titanium, and B) an activator.

9. The olefin polymerization catalyst system according to claim 8, characterized in that the activator is selected from the group consisting of an aluminoxane; an organoaluminum compound; an ionic activator; and mixtures thereof.

10. The olefin polymerization catalyst system according to claim 8, characterized in that R1' is unsubstituted adamantyl or substituted adamantyl.

11. The olefin polymerization catalyst system according to claim 8, characterized in that R1' is unsubstituted adamantyl.

12. The olefin polymerization catalyst system according to claim 11, characterized in that each R1 is unsubstituted adamantyl.

13. The olefin polymerization catalyst system according to claim 11, characterized in that R1' and each R1 is 1-adamantile.

14. The olefin polymerization catalyst system according to any of claims 10-13, characterized in that Cp is (pentamethyl)cyclopentadienyl.

15. The olefin polymerization catalyst system according to any of claims 10-13, characterized in that Cp is cyclopentadienyl.

16. 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 according to any of claims 10-15 under polymerization conditions.

17. The process according to claim 16, 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.

18. 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 alpha Ln / Zznz / E / YIAI C3 to C10 olefins, in a solvent in a first polymerization reactor at a temperature of 80 to 200°C and a pressure from 6894.76 kPa to 55,158.07 kPa (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 alpha C3-C10 olefins, in the presence of a Ziegler Naphtha catalyst.