Methods for making trihydrocarbyl phosphines, pre-metallation compounds and single site polymerization catalysts

Abstract

Provided are synthetic methods to make trihydrocarbyl phosphines and phosphinimine pre-metallation compounds which may be used to make single site polymerization catalysts.

Description

[0001] METHODS FOR MAKING TRIHYDROCARBYL PHOSPHINES, PRE-METALLATION COMPOUNDS AND SINGLE SITE POLYMERIZATION CATALYSTS TECHNICAL FIELD Synthetic methods for the preparation of trihydrocarbyl phosphines and phosphinimine pre-metallation compounds are provided. The phosphinimine pre- metallation compounds afford highly active single site polymerization catalysts on reaction with a group 4 metal compound. BACKGROUND ART Highly active single site olefin polymerization catalysts were disclosed in WO 2023 / 187552. SUMMARY OF INVENTION Provided is a method for making a trihydrocarbyl phosphine compound having the formula I, , (a) combining a compound having the formula II, a Grignard reagent, RMgCl, then with ZnCl2 and then with PCl3 to the formula III, ; (b) combining the compound having the formula III with a Grignard reagent, R1MgCl in the presence of copper iodide, CuI and lithium bromide, LiBr to provide a compound having the formula IV, ; compound having the formula IV with an organolithium a compound having the formula V, the having the formula I; wherein R is a C1-20 alkyl group; wherein R* is a C1-20alkyl group; wherein R1is a primary alkyl group, or a secondary alkyl group, or a tertiary alkyl group; wherein R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; a fluorine atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; wherein X is I or Br; and wherein X* is I or Br. Provided is a method for making a pre-metallation compound having the formula PM-I-H, , the having the formula I ), with an up consisting of Br2, Cl2, and Cl3C-CCl3; and then with ammonia, NH3; and optionally then with a base to provide the pre-metallation compound having the formula PM-I-H; wherein R1is a primary alkyl group, or a secondary alkyl group, or a tertiary alkyl group; wherein R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; a fluorine atom; a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group. DESCRIPTION OF EMBODIMENTS As used herein, the term “monomer” refers to a small molecule that may chemically react and become chemically bonded with itself or other monomers to form a polymer. As used herein, the term “α-olefin” or “alpha-olefin” is used to describe a monomer having a linear hydrocarbon chain containing from 3 to 20 carbon atoms having a double bond at one end of the chain; an equivalent term is “linear α-olefin”. As used herein, the term “polyethylene” or “ethylene polymer”, refers to macromolecules produced from ethylene monomers and optionally one or more additional monomers; regardless of the specific catalyst or specific process used to make the ethylene polymer. In the polyethylene art, the one or more additional monomers are called “comonomer(s)” and often include a- olefins. The term “homopolymer” refers to a polymer that contains only one type of monomer. An “ethylene homopolymer” is made using only ethylene as a polymerizable monomer. The term “copolymer” refers to a polymer that contains two or more types of monomer. An “ethylene copolymer” is made using ethylene and one or more other types of polymerizable monomer. Common polyethylenes include high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultralow density polyethylene (ULDPE), plastomers and elastomers. The term polyethylene also includes polyethylene terpolymers which may include two or more comonomers in addition to ethylene. The term polyethylene also includes combinations of, or blends of, the polyethylenes described above. As used herein, the terms “hydrocarbyl”, “hydrocarbyl radical” or “hydrocarbyl group” refers to linear, branched, cyclic, acyclic, aliphatic, olefinic (i.e., has double bond unsaturation), acetylenic (i.e., has triple bond unsaturation) and aryl (aromatic) groups comprising hydrogen and carbon that are deficient by at least one hydrogen atom. Hence a person skilled in the art will understand that “hydrocarbyl group” includes by way of providing non-limiting examples, alkyl groups, which may be primary, secondary (such as for example a cycloalkyl group), or tertiary alkyl groups; alkenyl groups; alkynyl groups; and aryl groups. The term “cyclic hydrocarbyl group” is a subset of the term “hydrocarbyl group” and specifically connotes hydrocarbyl groups that comprise at least one cyclic moiety and which may have one or more than one aromatic ring, and / or one or more than one non-aromatic ring present within them. The term “acyclic hydrocarbyl group” is a subset of the term “hydrocarbyl group” and specifically connotes 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 bound to carbon. The term “heteroatom containing” or “heteroatom containing hydrocarbyl group” means that one or more than one non carbon atom, not including a hydrogen atom, is present in the hydrocarbyl group. Some non-limiting examples of non-carbon atoms (and non-hydrogen atoms) that may be present is a heteroatom containing hydrocarbyl group are N, O, S, P and Si as well as halides such as for example F and / or Br as well as metals such as Sn. Some non-limiting examples of heteroatom containing hydrocarbyl groups include for example aryloxy groups, alkoxy groups, alkylaryloxy groups, arylalkyloxy, silyl groups, and siloxy groups. Further non- limiting examples of heteroatom containing hydrocarbyl groups generally include for example imines, amine moieties, oxide moieties, phosphine moieties, ethers, ketones, heterocyclics, oxazolines, thioethers, and the like. The term “cyclic heteroatom containing hydrocarbyl group” is a subset of the term “heteroatom containing hydrocarbyl group” and specifically connotes heteroatom containing hydrocarbyl groups that comprise at least one cyclic moiety and which may have one or more than one aromatic ring, and / or one or more than one non-aromatic ring present within them. The term “acyclic heteroatom containing hydrocarbyl group” is a subset of the term “heteroatom containing hydrocarbyl group” and specifically connotes heteroatom containing hydrocarbyl groups that do not have cyclic moieties such as aromatic or non-aromatic ring structures present within them. In an embodiment of the disclosure, a heteroatom containing hydrocarbyl group is a hydrocarbyl group containing from 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur. In an embodiment of the disclosure, a cyclic heteroatom containing hydrocarbyl group is a cyclic hydrocarbyl group containing from 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur. The term “heterocyclic group” is a subset of the term “cyclic heteroatom containing hydrocarbyl group” and specifically refers to ring systems having a carbon backbone that further comprises at least one heteroatom selected from the group consisting of for example boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur within a ring structure. As used herein, an “alkyl radical” or “alkyl group” includes linear, branched and cyclic paraffin groups that are deficient by one hydrogen group; non-limiting examples include methyl (-CH3) and ethyl (-CH2CH3) groups, which are non-limiting examples of primary alkyl groups; iso-propyl and cyclohexyl groups, which are non-limiting examples of secondary alkyl groups; and a tert-butyl group, which is a non-limiting example of a tertiary alkyl group. 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 by one hydrogen group. 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 by one hydrogen group. As used herein, the term “aryl radical” or “aryl group” includes phenyl, naphthyl, pyridyl and other groups whose molecules have an aromatic ring structure; non-limiting examples include naphthalene, phenanthrene and anthracene. An “arylalkyl” is a subset of an “alkyl group” and is an alkyl group having an aryl group pendant there from; non-limiting examples include benzyl, phenethyl and tolylmethyl. An “alkylaryl” group is a subset of an “aryl group” and is an aryl group having one or more alkyl groups pendant there from; non-limiting examples include tolyl, xylyl, mesityl and cumyl. An “alkoxy group” is an oxy group having an alkyl group pendant there from; and includes for example a methoxy group, an ethoxy group, an iso-propoxy group, and the like. An “arylalkyloxy group” is an oxy group having an arylalkyl group pendent there from (for clarity, the alkyl moiety is bonded to the oxy moiety and the aryl group is bonded to the alkyl moiety). An “aryloxy” group is an oxy group having an aryl group pendant there from; and includes for example a phenoxy group and the like. An “alkylaryloxy group” is an oxy group having an alkylaryl group pendent there from (for clarity, the aryl moiety is bonded to the oxy moiety and the alkyl group is bonded to the aryl moiety). In the present disclosure, a hydrocarbyl group or a heteroatom containing hydrocarbyl group (or subsets of these groups, such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, etc.) may be further specifically defined as being unsubstituted or substituted. As used herein the term “unsubstituted” means that hydrogen groups are bounded to the molecular group that is referred to by the term unsubstituted. The term “substituted” means that the group referred to by this term possesses one or more moieties that have replaced one or more hydrogen groups in any position within the group; non- limiting examples of moieties include halogen groups (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, C1to C10alkyl groups, C2 to C10 alkenyl groups, and combinations thereof. In embodiments of the disclosure, any hydrocarbyl group and / or any heteroatom containing hydrocarbyl group may be unsubstituted or substituted. In embodiments of the present disclosure, methods are provided to make trihydrocarbyl phosphine compounds. In embodiments of the present disclosure, methods are provided to make trihydrocarbyl phosphine compounds having an ortho substituted aryl group. In embodiments of the present disclosure, methods are provided to make phosphinimine pre-metallation compounds. In embodiments of the present disclosure, methods are provided to make single site polymerization catalysts (also known as pre-polymerization catalysts). The preparation of trihydrocarbyl phosphines (“tertiary” phosphines) by alkylation of phosphorus trichloride or trihydrocarbylphosphites with alkylating agents such as Grignard reagents or organolithium reagents is known. Alternatively, tertiary phosphines (including unsymmetrical tertiary phosphines which have different hydrocarbyl groups) may be prepared by employing organophosphorus based nucleophiles in a reaction with hydrocarbyl halides, such as for example, the reaction of a lithium dihydrocarbyl phosphide, LiPR2 with a hydrocarbyl halide such as an alkyl halide R’X to give trihydrocarbyl phosphine compounds with the general formula: R’PR2(where R’ and R are different hydrocarbyl groups). It is known that Grignard reagents having the general formula RMgX can be made by treating hydrocarbyl halides, RX with solid magnesium (e.g. magnesium ribbon). It is also known that Grignard reagents, R’MgX can be formed by transmetallation or “Mg exchange” type reactions between an already existing Grignard reagent, RMgX and a hydrocarbyl halide R’X. Similarly, hydrocarbyl group transfer between organozinc compounds having the general formula RZnR’ and solid magnesium or preformed Grignard reagents having the general formula RMgX is also well established. In an embodiment of the present disclosure a method for making a compound having the formula III, mprises combining a compound having the formula II, a Grignard reagent, RMgX€, and then with ZnCl2 and then with P wherein R is a C1-30 hydrocarbyl group; wherein R7, R8, R9, and R10are each independently selected from the group consisting of a hydrogen atom; a fluorine atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R7, R8, R9, and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; wherein X is I or Br; wherein X* is I, Br or Cl; and wherein X€is I, Br, or Cl. In embodiments, X is Br. In embodiments, X* is Br or I. In embodiments, X* is Br. In embodiments, X€is Cl. In embodiments, R is a C1-20alkyl group. In embodiments, R is an iso-propyl group. In embodiments, R is a tert-butyl group. In embodiments, R is a cyclohexyl group. In embodiments, R7, R8, R9, and R10are each independently selected from the group consisting of a hydrogen atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; wherein two adjacent groups of R7, R8, R9, and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group. In embodiments R7, R8, R9, and R10are each independently selected from the group consisting of a hydrogen atom; and a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; wherein two adjacent groups of R7, R8, R9, and R10may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, a C7-20arylalkyloxy group. In embodiments R7, R8, R9, and R10are each independently selected from the group consisting of a hydrogen atom; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group. In embodiments R7, R8, R9, and R10are hydrogen. Without wishing to be bound by theory, it is speculated that use of the zinc chloride reagent, ZnCl2 helps to facilitate a more selective arylation of the trichlorophosphine: by reaction of the compound having the formula II with the Grignard reagent, RMgX€to provide an aryl Grignard reagent, which on reaction with ZnCl2 provides which then reacts with only once. In embodiments of the disclosure a molar excess of PCl3is used relative to the compound having the formula II. In an embodiment of the present disclosure a method for making a compound having the formula IV, III, In embodiments, R1is C1-30 primary alkyl group or a C3-30 secondary alkyl group. In embodiments, R1is a secondary alkyl group. In embodiments, R1is a C3-30 secondary alkyl group. In embodiments, R1is an iso-propyl group or a cyclohexyl group. In embodiments, R1is a cyclohexyl group. In embodiments, R1is an iso-propyl group. In an embodiment of the present disclosure a method for making a compound having the formula IV, III, wherein R1is a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group; wherein X£is I, Br, or Cl; wherein X¥is I, Br, Cl, or F; and wherein R7, R8, R9, R10, X and X€are as defined in the embodiments above. In embodiments, R1is a C1-30primary alkyl group, a C3-30secondary alkyl group, or a C4-30 tertiary alkyl group In embodiments, R1is a secondary alkyl group or a tertiary alkyl group. In embodiments, R1is a C3-30 secondary alkyl group or a C4-30 tertiary alkyl group. In embodiments, R1is a secondary alkyl group. In embodiments, R1is a C3-30 secondary alkyl group. In embodiments, R1is a tertiary alkyl group. In embodiments, R1is a C4-30 tertiary alkyl group. In embodiments, R1is an iso-propyl group, a cyclohexyl group or a tert-butyl group. In embodiments, R1is a cyclohexyl group. In embodiments, R1is an iso-propyl group. In embodiments, R1is a tert-butyl group. In embodiments, X£is I. In embodiments, X¥is Br. In embodiments, the Grignard reagent, R1MgX€is combined with the compound having the formula III in a molar ratio of at least about 2. In embodiments, the Grignard reagent, R1MgX€is combined with the compound having the formula III in a molar ratio of about 2. In embodiments, the copper halide, CuX£, and the lithium halide, LiX¥, are used in catalytic amounts. That is, they are used in sub-stoichiometric amounts (less than in a 1:1 molar ratio) relative to the amount of the compound having the formula (III) and relative to the Grignard reagent, R1MgX€. Without wishing to be bound by theory, addition of a catalytic amount of copper halide, such as for example, CuI facilitates the transfer of the R1group from the Grignard reagent R1MgX€to the phosphorus atom by forming catalytic amounts of an organocuprate species having an R1-Cu bond. Without wishing to be bound by theory, the inclusion of catalytic amounts of a lithium halide, such as for example, LiBr may facilitate the formation of lower-order organocuprates, also known as Gilman reagents, having the formula R12CuLi. Lithium halide exchange reactions are known in the art and have been discussed in for example J. Organomet. Chem.1988, 352, 1–46 and Organometallics 2006, 25, 2–24. In a lithium halide exchange reaction, an organohalide compound R-X is reacted with an organolithium reagent, LiR’. The halogen group, X in a lithium halide exchange reaction is generally Br or I, and the R group of the organohalide compound is generally an aryl group. In an embodiment of the present disclosure a lithium halide exchange reaction combines a compound having the formula IV, organolithium compound, R*Li, to give a compound having ; group; and are as defined in the embodiments above. In an embodiment, the compound having the formula IV-Li is used in further reaction chemistry without being isolated from solution. In an embodiment, after lithium halide exchange, to give the compound having the formular IV-Li, the compound having the formula IV-Li is reacted, in a nucleophilic attack reaction, with an unsubstituted or a substituted fluorenone compound. In an embodiment of the disclosure, the organolithium compound having the formula III-Li is not isolated from solution and is reacted with an unsubstituted or a substituted fluorenone compound. In an embodiment of the disclosure, the organolithium compound having the formula IV-Li is combined with a fluorenone compound having the formula V, give a compound having the formula VI-OLi, ); defined in the embodiments above; wherein R , R , R , R , R , R , R17and R18are each independently selected from the group consisting of a hydrogen atom; a fluorine atom; a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group. In an embodiment R* is a C1-20alkyl group. In an embodiment R* is n-butyl. In an embodiment R* is tert-butyl. In an embodiment, the compound VI-OLi is isolated from solution. In an embodiment, the compound VI-OLi is used in further reaction chemistry without being isolated from solution. In embodiments of the disclosure, the nucleophilic attack reaction is done in situ. That is, the compound having the formular IV-Li is not isolated before its combination with the fluorenone compound having the formula V, be converted to an alcohol through a hydrolysis reaction to give a compound having formula VI-OH, , wherein R1, R7, R8, R9, R10, R11, R12, R13, embodiments above. In an embodiment, the compound having the formula VI-OH is isolated from solution. In an embodiment, the compound having the formula VI-OH is used in further reaction chemistry without being isolated from solution. In embodiments, R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group. In embodiments R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; and a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20arylalkyloxy group. In embodiments R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group. In embodiments, each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is independently a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group. In embodiments, each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is independently a C1-20 alkyl group. In embodiments, each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is a tert-butyl group. In embodiments, each of R11, R14, R15, and R18is a hydrogen atom and R12, R13, R16and R17are each independently a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R12, R13, R16and R17may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group. In embodiments, each of R11, R14, R15, and R18is a hydrogen atom and R12, R13, R16and R17are each independently a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group. In embodiments, each of R11, R14, R15, and R18is a hydrogen atom and R12, R13, R16and R17are each independently a C1-20alkyl group. In embodiments, each of R11, R14, R15, and R18is a hydrogen atom, and adjacent groups of R12and R13, and adjacent groups of R16and R17are: marks the point of attachment to adjacent fluorenyl group carbon atoms. In embodiments R11, R12, R13, R14, R15, R16, R17and R18are hydrogen. Direct methods to reduce alcohols are not general, which is why alcohols may be usefully employed as solvents for hydrogenation reactions of other functional groups using a reducing agent. However, alcohols and near derivatives can be reduced under certain conditions, especially if the -OH group is first converted to, for example, a sulfonate group (by for example, treatment with methanesulfonyl chloride, ClSO2Me or tosyl chloride, ClSO2-p-toluene). Examples of well- known reducing agents which can be used in embodiments of the disclosure include hydrogen, H2; lithium aluminum hydride, LiAlH4; and sodium borohydride, NaBH4. Additional, known reducing agents which may be used in embodiments of the disclosure include those selected from the group consisting of AlH3 (or AlH3∙SMe2), BH3(or BH3∙SMe2), di-isobutylaluminum hydride, LiAlH(OMe)3, LiEt3BH, Bu3SnH, NaAlEt2H2, (EtO)3SiH, PhSiH3, O(SiHMe)2, and polymethylhydrosiloxane (PHMS). Optionally, and in embodiments of the disclosure, a reducing agent can be using in combination with a catalyst, such as a catalyst selected from the group consisting of a group 4 metal catalyst, such as a group 4 metal halide (e.g. TiCl4(THF)2); a platinum catalyst; a palladium catalyst; an iron catalyst; or a nickel catalyst (such as, for example, a Raney nickel catalyst). Optionally, and in embodiments of the disclosure, a reducing agent can be used in combination with trifluoromethanesulfonic anhydride, “triflic anhydride”, (CF3SO2)2O or trifluoromethane sulfonic acid, “triflic acid”, CF3SO2H. In an embodiment of the disclosure, a method for making a trihydrocarbyl phosphine compound having the formula I, VI- wherein R1, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are as defined in the embodiments above. In an embodiment of the disclosure, a method for making a trihydrocarbyl phosphine compound having the formula I, wherein R1, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are as defined in the embodiments above. In an embodiment of the disclosure, a method for making a trihydrocarbyl phosphine compound having the formula I, wherein R1, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are as defined in the embodiments above. In an embodiment of the disclosure, a method for making a trihydrocarbyl phosphine compound having the formula I, ; comprises combining a compound having the formula VI- ); F3SO2)2O; wherein R, R, R, R, R , R , R , R13, R14, R15, R16, R17and R18are as defined in the embodiments above. In an embodiment of the disclosure, a method for making a trihydrocarbyl phosphine compound having the formula I,

[0002] nd then combining the compound having the for wherein R is a methyl group or a para-methyl-phenyl group; and wherein R1, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are as defined in the embodiments above. In an embodiment of the disclosure, a method for making a trihydrocarbyl phosphine compound having the formula I, nd then combining the compound having the for wherein R, R, R, R, R , R , R , R , R14, R15, R16, R17and R18are as defined in the embodiments above. In an embodiment of the disclosure, a method for making a trihydrocarbyl phosphine compound having the formula I, nd then combining the compound having the for wherein R is a methyl group or a para-methyl-phenyl group; and wherein R1, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are as defined in the embodiments above. In embodiments, a reducing agent such as for example, LiAlH4is used in a molar excess relative to the compound having the formula VI-OLi, or VI-OH, or VI-S (i.e. in a molar ratio of greater than about 1). In embodiments, a reducing agent such as for example, LiAlH4 is combined with the compound having the formula VI-OLi, or VI-OH, or VI-S in a molar ratio of at least about 1:1, or at least about 4:1, or at least about 8:1, or least about 10:1. In embodiments, the triflic anhydride, (CF3SO2)2O is combined with the compound having the formula VI-OLi in a molar ratio of about 1:1. In embodiments, a molar excess of the triflic anhydride, (CF3SO2)2O is combined with the compound having the formula VI- OLi (i.e. in a molar ratio of greater than about 1). In embodiments, catalytic amounts of TiCl4 or TiCl4(THF)2 are used in combination with a reducing agent. Hence, in embodiments, TiCl4or TiCl4(THF)2are used in sub- stoichiometric amounts (less than in a 1:1 molar ratio) relative to the amount of the compound having the formula VI-OLi (or VI-OH, or VI-S). Methods for making a trihydrocarbyl phosphinimine moiety, such as t-Bu3P=N-X3where X3is H or trimethylsilyl (“TMS”), from t-Bu3P are known. For example, in one well known method, t-Bu3P is combined with trimethyl silyl azide, N3-SiMe3 (see for example, Organometallics 2003, 22, 818). Although this reaction is effective for producing t- Bu3P=N-TMS which can be used to make highly active single site polymerization catalysts, so called “phosphinimine single site catalysts” or “phosphinimide single site catalysts”, accessing the pre-metallation compound in this manner requires the use of a potentially shock sensitive azide compound. Other methods of oxidizing t-Bu3P to a phosphinimine pre-metallation compound are also known and include for example treatment of t-Bu3P with chlorine gas, Cl2followed by ammonia, to give t-Bu3P=N-H∙HCl, which can be treated with a base and TMS-Cl to afford t-Bu3P=N-TMS. Phosphinimine pre-metallation compounds have also been prepared from trihydrocarbyl phosphine compounds having an ortho substituted phenyl group by reaction with hexachloroethane, Cl3C-CCl3and then hexamethyldisilazane, [(CH₃)₃Si]₂NH, as discussed in WO 2023 / 187552. In an embodiment of the present disclosure, a phosphinimine pre-metallation compound is accessed using a variation of this chemistry. In an embodiment, a method for making a pre-metallation compound having the formula PM-I-H, , compound having the formula I , with consisting of Br2, Cl2, and hexachloroethane, Cl3C- CCl3; and then with ammonia, NH3; and optionally then with a base to provide the pre- metallation compound having the formula PM-I-H; where R1, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are as defined in the embodiments above. In an embodiment, a method for making a pre-metallation compound having the formula PM-I-H,

[0003] ), compri hine compound having the formula I hexachloroethane, Cl3C-CCl3 and then with base to provide the pre-metallation compound having the formula PM-I-H; where R1, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are as defined in the embodiments above. In embodiments, the trihydrocarbyl phosphine compound having the formula I and the hexachloroethane, Cl3C-CCl3, are combined in a molar ratio of about 1:1. In embodiments, a molar excess of ammonia, NH3 is combined with the reaction product formed by combining the trihydrocarbyl phosphine compound having the formula I with hexachloroethane, Cl3C-CCl3. In embodiments, a molar excess of ammonia, NH3is combined with the reaction product formed by combining the trihydrocarbyl phosphine compound having the formula I with an oxidant selected from the group consisting of Br2, Cl2, and hexachloroethane, Cl3C- CCl3. In embodiments, the amount of ammonia, NH3used can be in the range of about 0.5 to about 10 moles of ammonia per 1 mole of the trihydrocarbyl phosphine compound having the formula I. In embodiments, the amount of ammonia, NH3used can be in the range of at least about 1.0 mole of ammonia per 1 mole of the trihydrocarbyl phosphine compound having the formula I. In further embodiments, the amount of ammonia, NH3 used can be in the range of at least about 1.0 mole of ammonia, or at least 2.0 moles of ammonia, or at least 3.0 moles of ammonia, or at least 5.0 moles of ammonia, or at least 10 moles of ammonia per 1 mole of the trihydrocarbyl phosphine compound having the formula I. In embodiments, a molar ratio of the ammonia, NH3to the reaction product formed by the combination of the trihydrocarbyl phosphine compound having the formula I with hexachloroethane, Cl3C-CCl3is greater than 1.0, or equal to or greater than 1.5, or equal to or greater than 2.0, or equal to or greater than 2.5, or equal to or greater than 3.0, or equal to or greater than 3.5, or equal to or greater then 4.0, or equal to or greater then 4.5, or equal to or greater than 5.0, or from about 1.5 to about 5.0, or from about 1.5 to about 4.5, or from about 1.5 to about 4.0, or from about 2.0 to about 4.0, or from about 2.5 to about 3.5. In embodiments, a base is added to a reaction product formed by the combination of the trihydrocarbyl phosphine compound having the formula I, the hexachloroethane, Cl3C- CCl3; and ammonia, NH3, in order to give a compound represented by formula PM-I-H. In embodiments, a base is added to a reaction product formed by the combination of i) the trihydrocarbyl phosphine compound having the formula I; ii) an oxidant selected from the group consisting of Br2, Cl2, and hexachloroethane, Cl3C-CCl3; and iii) ammonia, NH3, in order to give a compound represented by formula PM-I-H. In embodiments, the base that may be used following treatment with NH3for production of the phosphinimine pre-metallation compound having the formula PM-I-H includes organic alkali metal compounds, such as for example, organolithium compounds such as methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilylacetylide, lithium acetylide, trimethylsilylmethyl lithium, vinyl lithium, phenyl lithium and allyl lithium. In embodiments, the base that may be used following treatment with NH3for production of the phosphinimine pre-metallation compound having the formula PM-I-H includes alkali metal alkoxide compounds, alkali metal phenoxide compounds or alkali metal hydroxides. In an embodiment the base used following treatment with NH3 for production of the phosphinimine pre-metallation compound having the formula PM-I-H is a lithium alkoxide compound. In an embodiment the base used is lithium iso-propoxide. In embodiments, the base that may be used following treatment with NH3for production of the phosphinimine pre-metallation compound having the formula PM-I-H may be another base (i.e. other than the NH3reagent itself). In some embodiments, the base may be an amine compound. Such an amine compound includes primary amine compounds such as methylamine, ethylamine, n- propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline and ethylenediamine, secondary amine compounds such as dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n- decylamine, pyrrolidine, hexamethyldisilazane and diphenylamine, and tertiary amine compounds such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenylamine, N,N- dimethylaniline, Ν,Ν,Ν',Ν'-tetramethylethylenediamine, N-methylpyrrolidine and 4- dimethylaminopyridine. In embodiments, the amount of the base used can be a range of 0.5 to 5 moles of base per 1 mole of the trihydrocarbyl phosphine compound having the formula I. In further embodiments, the amount of the base used can be a range of 1.0 to 3.0 moles of base per 1 mole of the trihydrocarbyl phosphine compound having the formula I; or can be in a range of 1.5 to 2.5 moles of base per 1 mole of the trihydrocarbyl phosphine compound having the formula I; or can be a range of 1.8 to 2.3 moles of base per 1 mole of the trihydrocarbyl phosphine compound having the formula I; or about 2 moles of base per 1 mole of the trihydrocarbyl phosphine compound having the formula I. In embodiments, the pre-metallation compound having the formula PM-I-H may be used in a further chemical reaction without first being isolated from solution. Methods to metallate phosphinimine ligand precursors (such as the pre-metallation compounds discussed above) with group 4 metals to provide organometallic complexes which are useful as pre-polymerization catalysts are well established (see for example, Organometallics 1999, 18, 1116 and WO 2023 / 187552). Such pre-polymerization catalysts are also known as “single site catalysts” or “single site polymerization catalysts”. The term “single site catalyst” is used herein to distinguish their polymerization behavior from polymerization catalysts which are traditionally considered multisite polymerization catalysts such as Ziegler-Natta catalysts or chromium-based catalysts. Persons skilled in the art will understand, for example, that metallocene catalysts, constrained geometry catalysts, and phosphinimine catalysts, are all generally considered “single site catalysts”. Metallation reactions may involve electrophilic abstraction of labile leaving groups from suitable group 4 metal precursors, and may involve, for example, the electrophilic abstraction of a halogen atom from a group 4 metal halide compound. Alternatively, metalation reactions may involve protonolysis of labile leaving groups from suitable group 4 metal precursors. Metallation pathways may involve an initial deprotonation step (i.e. deprotonation of one or more sites of the pre-metallation compound) using, for example, an organolithium reagent, followed by halide abstraction from group 4 metal precursors, or metalation may be carried out directly, when protonolysis of a labile leaving group from a group 4 metal precursor is possible. In embodiments of the disclosure, a pre-metallation compound having the formula PM-I-H is metalated by a direct or indirect reaction with MX14 or MX14(THF)2; wherein M is Ti, Zr, or Hf; and wherein each X1is independently selected from a protonolyzable group or a group which can be abstracted by electrophilic abstraction. In an embodiment of the disclosure a metallation reaction with a group 4 metal compound, MX14 or MX14(THF)2 can proceed by direct protonolysis by the pre-metallation compound having the formula PM-I-H where at least one and preferably two of X1is / are a protonolyzable group. Examples of protonolyzable groups, X1, may in embodiments of the disclosure include an amido group of the formula -NR€2 wherein each R€is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group. In another embodiment of the disclosure a metallation reaction with a group 4 metal compound, MX14or MX14(THF)2can proceed by the deprotonation, preferably the double deprotonation of the pre-metallation compound having the formula PM-I-H using a base, followed by electrophilic abstraction of at least one and preferably two X1group / groups. Examples of groups, X1which can be electrophilically abstracted, may in embodiments of the disclosure include a halide, an C1-20alkoxy group, an C6-20aryloxy group, an C7-20alkylaryloxy group, and an C7-20 arylalkyloxy group. In embodiments, each X1is independently selected from a chloride, a dimethylamido group and a diethylamido group. In embodiments, each X1is a halide. In embodiments, each X1is a dimethylamido group or a diethylamido group. In embodiments each X1is chloride. In embodiments, the base used to carry out the deprotonation or double deprotonation of the pre-metallation compound having the formula PM-I-H is selected from organic alkali metal compounds, such as for example, organolithium compounds which include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilylacetylide, lithium acetylide, trimethylsilylmethyl lithium, vinyl lithium, phenyl lithium and allyl lithium. In embodiments, the base used to carry out the deprotonation or double deprotonation of the pre-metallation compound having the formula PM-I-H is n-butyl lithium or tert-butyl lithium. In some embodiments, the base may be used in combination with an amine compound. Such an amine compound includes primary amine compounds such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline and ethylenediamine, secondary amine compounds such as dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-tert- butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane and diphenylamine, and tertiary amine compounds such as trimethylamine, triethylamine, tri-n- propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenylamine, N,N-dimethylaniline, Ν,Ν,Ν',Ν'-tetramethylethylenediamine, N- methylpyrrolidine and 4-dimethylaminopyridine. In alternative embodiments of the disclosure, a pre-metallation compound having the formula PM-1, is metalated by reaction with MX*4 or MX*4 wherein M is Ti, Zr, or Hf; wherein R1, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are as defined in the embodiments above; wherein each X* is independently selected from a halide (preferably a chloride), an C1-20 alkoxy group, an C6-20 aryloxy group, an C7-20 alkylaryloxy group, an C7-20 arylalkyloxy group, and an amido group of the formula -NR€2wherein each R€is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group (e.g. a dimethylamido group or a diethylamido group); X2is hydrogen, or a silyl group of the formula -Si(Re)3, X3is hydrogen, or a silyl group of the formula -Si(Re)3; wherein each Reis independently selected from the group consisting of hydrogen, a C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and a C6-20 aryl group. In some embodiments, X2is hydrogen. In some embodiments, X2is a silyl group of the formula -Si(Re)3, wherein each Reis independently selected from the group consisting of hydrogen, C1-8alkyl group, C1-8alkoxy group, C6-20 aryloxy group and C6-20 aryl group. In some embodiments, X2is -Si(Me)3. In some embodiments, X3is hydrogen. In some embodiments, X3is a silyl group of the formula -Si(Re)3, wherein each Reis independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20aryloxy group and C6-20aryl group. In some embodiments, X3is -Si(Me)3. In an embodiment of the disclosure, a metallation reaction (of for example, the pre- metallation compound having the formula PM-1) with a group 4 metal compound, MX*4 or MX*4(THF)2 can proceed by direct protonolysis of a leaving group where X2and / or X3is hydrogen and where X* is a protonolyzable group. Examples of protonolyzable groups, can in embodiments of the disclosure include an amido group of the formula -NR€2 wherein each R€is independently selected from the group consisting of hydrogen, C1-20alkyl group, and C6-20 aryl group. Alternatively, in an embodiment of the disclosure a metallation reaction (of for example, the pre-metallation compound having the formula PM-1) with a group 4 metal compound, MX*4or MX*4(THF)2can proceed by abstraction of a leaving group where X2and / or X3is a trimethyl silyl group, -Si(Me)3 and where X* is a group which can be removed by electrophilic abstraction. Examples of groups, X* which can be abstracted in embodiments of the disclosure include halide or alkoxy groups. In an embodiment X* is chloride. In another embodiment of the disclosure a metallation reaction (of for example, the pre-metallation compound having the formula PM-1) with a group 4 metal compound, MX*4 or MX*4(THF)2 can proceed by deprotonation using a base where X2and / or X3are hydrogen, followed by abstraction of a leaving group where X* is a group which can be removed by electrophilic abstraction. Examples of groups, X* which can be abstracted in embodiments of the disclosure include halide or alkoxy groups. In an embodiment X* is chloride. In embodiments, each X* is independently selected from a chloride, a dimethylamido group and a diethylamido group. In embodiments, each X* is a halide. In embodiments, each X* is a dimethylamido group or a diethylamido group. In embodiments each X* is chloride. In embodiments, the base used to carry out the deprotonation reaction where X2and / or X3are hydrogen, is selected from organic alkali metal compounds, such as for example, organolithium compounds which include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilylacetylide, lithium acetylide, trimethylsilylmethyl lithium, vinyl lithium, phenyl lithium and allyl lithium. In embodiments, the base used to carry out the deprotonation reaction where X2and / or X3are hydrogen, is n-butyl lithium or tert-butyl lithium. In some embodiments, the base may be used in combination with an amine compound. Such an amine compound includes primary amine compounds such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline and ethylenediamine, secondary amine compounds such as dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-tert- butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane and diphenylamine, and tertiary amine compounds such as trimethylamine, triethylamine, tri-n- propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenylamine, N,N-dimethylaniline, Ν,Ν,Ν',Ν'-tetramethylethylenediamine, N- methylpyrrolidine and 4-dimethylaminopyridine. Representative, non-limiting examples of metallation reactions which can be used in embodiments of the present disclosure to make organometallic complexes which may serve as pre-polymerization catalysts include:

[0004] R R1312R14R13R14= R R1312R14= as defined in the embodiments above; = as defined in the embodiments above;

[0005] , wherein M = R17and R18are as defined in the embodiments above; and , wherein M = and R18are as defined in the embodiments above. A person skilled in the art will know that pre-polymerization catalysts having halide ligands may be transformed into pre-polymerization catalysts having alkyl ligands by treatment with alkylating reagents. For example, and in embodiments of the disclosure, a dichloride organometallic complex (e.g. a dichloride pre-polymerization catalyst) may be converted into a dimethyl organometallic complex (e.g. a dimethyl pre-polymerization complex) by treatment with an alkyl lithium reagent such as methyllithium or with a Grignard reagent such as methylmagnesium bromide as shown below: R7, above. Persons skilled in the art will understand that each of the forgoing chemical reactions can be carried out in a variety of solvents, including mixtures of different solvents. In embodiments of the disclosure a solvent or mixture of solvents can be selected from various polar and non-polar solvents, including aprotic solvents and a person skilled in the art will know how to select an appropriate solvent for a particular combination of reactants, or determine an appropriate solvent by routine experiment. Reaction solvents which can be used in embodiments of the disclosure include those selected from the group consisting of methanol, ethanol, dichloromethane, 1,2- dichloroethane, diethyl acetate, pyridine, acetone, dimethylformamide, dimethyl sulfoxide, acetonitrile, aromatic hydrocarbon solvents such as benzene or toluene, aliphatic hydrocarbon solvents such as hexane or heptane, ether solvents such as diethyl ether, tetrahydrofuran or 1,4-dioxane, amide solvents such as hexamethylphosphoric amide or dimethylformamide, propionitrile, diethyl ketone, methyl isobutyl ketone, cyclohexanone, chlorobenzene, and dichlorobenzene. In embodiments, these solvents may be used alone or as a mixture of two or more of them. Persons skilled in the art will understand that the forgoing chemical reactions can be carried out at ambient temperatures, temperatures above ambient temperature or they can be carried out at temperatures below ambient temperature. In embodiments, the compounds made in the forgoing chemical reactions may sometimes be isolated from a reaction mixture using conventional methods, such as, filtration, extraction, precipitation, crystallization, recrystallization, removing solvents under vacuum, washing with solvent or diluent, and the like, as well as combinations thereof. EXAMPLES General Experimental Methods All reactions involving air- and / or moisture-sensitive compounds were conducted under nitrogen using standard Schlenk techniques or in an inert atmosphere glovebox; reaction solvents were purified using the system described by Pangborn et al. (Pangborn, A. B. G.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics 1996, 15, 1518) and then stored over activated molecular sieves in an inert atmosphere glovebox. Solvents for air- and moisture-stable reactions were purchased from VWR and used as received. Deuterated solvents were purchased from CIL and stored over activated 13x molecular sieves. Celite®was purchased from Sigma-Aldrich, oven-dried, and stored in the glovebox for use with moisture-sensitive chemistry. Cesium fluoride (CsF) and zinc chloride were purchased from Sigma-Aldrich and were dried at 150°C under vacuum prior to use. Tetrakis(dimethylamido)titanium(IV) (Ti(NMe2)4) was purchased from Strem Chemicals and used as received. MMAO-7 (7 wt% solution in Isopar-E), diethylaluminum ethoxide (DEAL-E; 25 wt% in heptane), triethylaluminum (TEAL; 25 wt% in heptane), and triisobutylaluminum (TIBAL; 25 wt% solution in hexanes) were purchased from Nouryon and used as received. Triphenylcarbenium tetrakis(pentafluorophenyl)borate, (Ph3C)[B(C6F5)4], abbreviated TB herein, was purchased from Albemarle Corp. and used as received. Di(hydrogenated tallow)methylammonium (‘Armeenium’) tetrakis(pentafluorophenyl)borate (11.0 wt% in methylcyclohexane), abbreviated AB herein, was purchased from Boulder Scientific. All other reagents were purchased from Sigma-Aldrich and used as received. Ti(NMe2)2Cl2was prepared following the procedure in Wang, C.; Erker, G.; Kehr, G.; Wedeking, K.; Fröhlich, R. Organometallics 2005, 24, 4760. 2,7-di-tert-butyl-9H-fluoren-9-one can be purchased from Ambeed Inc. This compound can also be synthesized as described below. 3,3′-dibromo-5,5′,6,6′,7,7′,8,8′-octahydro-5,5,5′,5′,8,8,8′,8′-octamethyl-2,2′- Binaphthalene was prepared according to the procedures described in Journal of Photochemistry & Photobiology A: Chemistry 2019, 382, 111882. NMR spectra were recorded on a Bruker 400 MHz spectrometer (400.1 MHz for1H, 162 MHz for31P). Molecular weight (GPC-RI Mw, Mn and Mz in g / mol) and molecular weight distribution (GPC-RI Mw / Mn) data for continuous solution copolymerization experiments were obtained using conventional size exclusion (gel permeation) chromatography (SEC, or GPC). Accordingly, polymer sample solutions (1 to 2 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on 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 chromatographed at 140°C on a PL 220 high-temperature chromatography unit equipped with four Shodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate of 1.0 mL / minute, with a differential refractive index (DRI) as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect SEC columns from oxidative degradation. The sample injection volume was 200 µL. The SEC raw data were processed with the Cirrus GPC software. The SEC columns were calibrated with narrow distribution polystyrene standards. The polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in the ASTM standard test method D6474. In some cases, weight average molecular weights (GPC-IR4 Mw) are provided for copolymers produced in continuous solution copolymerization experiments using a different GPC instrument. Those were analyzed using a Polymer Char GPC-IR4 instrument equipped with three GPC columns to rapidly determine polymer Mw. Accordingly, a polymer sample (5 to 7 mg) was weighed into the sample vial and loaded onto the auto- sampler. The vial was filled with 6 ml 1,2,4-trichlorobenzene (TCB), heated to 160 °C with shaking for 160 minutes. 2,6-Di-tert-butyl-4-methylphenol (BHT) was added to the TCB in a concentration of 250 ppm to stabilize the polymer against oxidative degradation. Sample solutions were chromatographed at 140°C on the Polymer Char GPC-IR4 chromatography unit equipped with three GPC columns (e.g., PL Mixed B) using TCB as the mobile phase with a flow rate of 1.0 mL / minute, with an Infrared IR4 as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect SEC columns from oxidative degradation. The sample injection volume was 200 µL. The SEC raw data were processed using a Microsoft Excel macro. The SEC columns were calibrated with narrow distribution polystyrene standards. The polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in the ASTM standard test method D6474. FTIR branch frequencies (reported as CH3 / 1000C) were determined from a polymer plaque on a Thermo-Nicolet 750 Magna-IR Spectrophotometer using the method as described in the ASTM standard test method D6645. The polymer plaque is prepared using a compression molding device (Wabash-Genesis Series press) based on ASTM standard test method D1928 (currently replaced with D4703). Synthetic Methods 2,7-di-tert-butyl-9H-fluoren-9-one This synthesis is based by Sprinzak, Y. J. Am. Chem. Soc.1958, 80, 5449. a Flu (10.17 g, 36.5 mmol) in pyridine (150 mL), benzyltrimethylammonium hydroxide (3.05 g of 40 wt% solution in water, 7.0 mmol) and hydrogen peroxide (9.19 g of 30 wt% solution in water, 81.1 mmol) were added. The reaction mixture became bright yellow, and the mixture was stirred overnight at room temperature. The volatiles were removed under reduced pressure to afford a yellow solid which was extracted with pentane (3 x 50 mL). The pentane extracts were combined and dried over anhydrous sodium sulphate. The pentane solution was filtered through a fluted filter paper and the volatiles from the filtrate were evaporated to afford a yellow powder (10.29 g, 96.3% yield). NMR (CDCl3, ^, ppm),1H: 7.70 (m, 2H), 7.48 (m, 2H), 7.39 (m, 2H), 1.35 (s, 18H). (2-bromophenyl)dichlorophosphine To 1,2-dibromobenzene in THF (500 mL) cooled to 0°C for 15 minutes in a 3-necked 2-L round-bottomed flask equipped with an overhead stirrer connected to the Schlenk line was added isopropylmagnesium chloride (2.0 M in THF, 275 mL, 550 mmol) via cannula quantitatively with THF rinses (3 x 20 mL). The clear dark reaction mixture was stirred at 0°C for 2 hours. Anhydrous zinc chloride (71.547 g, 525 mmol) in THF (350 mL), a slightly turbid solution, added to the reaction via cannula, quantitatively with THF rinses (3 x 5 mL). The cold bath was removed and replaced with a lukewarm (35°C) water bath. After 10 minutes, the temperature of the bath had reached 19°C. The reaction mixture became turbid with the formation of a white suspended precipitate. This mixture containing the arylzinc reagent was taken into a glove box and slowly added as a slurry to phosphorus(III) chloride (137.32 g, 1000.0 mmol) in THF (200 mL) at ambient temperature, with vigorous stirring of the reaction mixture. The flask containing the arylzinc residue was rinsed with THF (2 x 50 mL) and the rinses added to the above reaction mixture. The resulting mixture was stirred for 15 minutes, and the volatiles removed under reduced pressure to give a white solid residue. The residue was extracted with heptane (2 x 400 mL) and filtered through a Celite-lined sintered-glass funnel, affording a clear colorless filtrate. The combined filtrate was evaporated to afford a clear, colorless, slightly viscous oil (108.164 g, 84% yield, ~95% pure by NMR). NMR (CDCl3, δ, ppm),1H: 7.99 (1H, dt, J = 7.8, 1.4 Hz, ArH), 7.47 (1H, ddd, J = 7.8, 4.8, 1.0 Hz, ArH), 7.40 (1H, t, J = 7.7 Hz, ArH), 7.27 (td, J = 7.6, 1.7 Hz, ArH).31P{1H}: 153.7. Compound 1 (2-Bromophenyl) 90.9 mmol) was diluted with heptane (300 mL) in a 500-mL Schlenk flask equipped with a large stir bar and cooled in an ice- water bath for 15 minutes. Isopropylmagnesium chloride (2.0 M in THF, 100 mL, 200 mmol) was added at a controlled rate to keep the temperature of the reaction under 10°C. A white precipitate gradually formed over the course of the addition.5 mins after reagent addition was complete, degassed MeOH (20 mL) was added to quench excess iPrMgCl and the resulting mixture was stirred for 15 minutes. Volatiles were removed under reduced pressure to give a solid residue, which was extracted with heptane (200 mL + 2 x 50 mL) and filtered through a medium porosity sintered-glass funnel, removing a white solid from the clear colorless filtrate. Removal of the solvents under reduced pressure afforded the product at ~85% purity (by31P NMR) as a hazy oil (20.727 g, 83% yield, 85% purity). Vacuum distillation of the hazy oil (135°C, 400 mTorr to 140°C, 300 mTorr) gave a colorless oil. NMR (toluene-d8, δ, ppm),1H: 7.39 (1H, ddd, J = 8.0, 3.1, 1.2 Hz, ArH), 7.10 (dt, J = 7.6, 1.4 Hz, ArH), 6.96 (td, J = 7.4, 1.2 Hz, ArH), 6.76 (td, J = 7.5, 1.6 Hz, ArH), 1.87 (2H, septet, J = 7.0 Hz, CHMe2), 1.04 (6H, dd, J = 14.0, 7.0 Hz, CHMe2), 0.83 (6H, dd, J = 14.0, 7.0 Hz, CHMe2).31P{1H}: 8.59. Compound 2 To Compound 1 (500 mL) and THF (22.55 g, 312.7 mmol) in a equipped with a stir bar, a Vigreux condenser and an addition funnel, was added nbutyllithium (1.6 M in hexanes, 195.5 mL, 312.7 mmol) (from the addition funnel) over 1 hour. This resulted in a yellow opaque heterogenous mixture. The reaction mixture was stirred for 2 hours and then added to a slurry of 2,7-di-tert-butyl-9H-fluoren-9-one (91.45 g, 312.7 mmol) in heptane (400 mL) in a 2-L round-bottomed flask equipped with a stir bar. A precipitate formed rapidly, and the reaction mixture was stirred overnight. The orange reaction mixture was filtered through a medium porosity sintered glass funnel and the filter cake was washed with heptane (3 x 20 mL) and pentane (2 x 20 mL), affording a white solid. The solid was dried under reduced pressure, affording the product (127.8 g, 84.6% yield). NMR (THF-d8, δ, ppm),1H: 9.06 (br m, 1H), 7.42 (d, J = 7.9 Hz, 2H), 7.36 (t, J = 7.2 Hz, 1H), 7.27 (d, J = 7.2 Hz, 1H), 7.17 (dd, J = 1.5 & 7.9 Hz, 2H), 7.19 (t, J = 7.0 Hz, 1H), 6.93 (s, 2H), 1.41 (m, 2 THF (~900 mL) forming a bright cherry red solution. After which, LiAlH4 (43.3 g, 1142.0 mmol) was added as a solid through a plastic funnel in 10 portions over the course of 50 minutes, during which the internal reaction temperature was maintained to 40-45°C (Rapid gas evolution was observed initially, and the reaction mixture turned a deep reddish brown colour. The mixture was heated at 60°C for 3 h. The reaction was allowed to cool to ambient temperature, sealed, taken to a fume hood and attached to a Schlenk line with a nitrogen bubbler and then cooled in an ice-water bath. A mixture of MeOH (230 mL, previously dried over sodium) and THF (~230 mL) was added through a cannula needle dropwise over the course of ~1 h. The mixture was allowed to warm to ambient temperature overnight with stirring. The volatiles were removed under reduced pressure to afford a grey-brown residue, which was extracted with toluene (900 mL + 200 mL) and filtered through a pad of Celite to give a light beige transparent filtrate. The toluene was removed under reduced pressure while the flask was heated at 45°C to give a beige powder (107.5 g, 80 %). NMR (toluene-d8, ^, ppm),1H: 7.70 (d, J = 8.0 Hz, 2H), 7.49 (m, 2H), 7.36 (m, 3H), 6.94 (ddd, J = 7.7, 6.1, 1.3 Hz, 1H), 6.79 (d, J = 13.0 Hz, 1H), 6.71 (ddd, J = 8.0, 7.5, 1.0 Hz, 1H), 6.52 (m, 1H), 2.08 (m, 2H), 1.24 (dd, J = 15.0, 6.8 Hz, 6H), 1.22 (s, 18H), 1.13 (dd, J = 11.3, 6.9 Hz, 6H). :31P{1H}: -6.8. METHOD B: To Compound 2 (1.0 g, 1.7 mmol) suspended in diethyl ether (~50 mL) was added very slowly trifluoromethanesulfonic anhydride (0.31 mL, 1.677 g / mL, 1.7 mmol) with 0.5wt% - 2.0wt% water. The reaction mixture became a translucent orange slurry and was stirred for 5 minutes. LiAlH4 (0.6 g, 16 mmol) was added in portions as a solid to the above reaction mixture over the course of 10 minutes. The resulting reaction mixture became a grey opaque slurry. The reaction was stirred for an additional 10 minutes, and the solvent and volatiles were removed under reduced pressure. The resulting grey residue was dissolved in toluene (~40 mL) and filtered. The volatiles from the filtrate were removed under reduced pressure to afford the product as a solid (0.67 g, 80% yield). Compound 4 Compound 3 (95.03 g, 201.9 mmol) was dissolved in 300 mL of dichloromethane in a 1000-mL 2-neck round bottom flask in a glove box. Separately, hexachloroethane (47.79 g, 201.9 mmol) was dissolved in 200 mL of dichloromethane in a 250-mL round bottom flask. The hexachloroethane solution was added to the phosphine solution slowly via a cannula at room temperature. The addition rate was controlled to keep the temperature of the mixture less than 35°C for 30 mins. Hexamethyldisilazane (132.9 mL, 605.7 mmol) was added to the reaction flask slowly in a similar fashion and stirred at room temperature overnight to form TMS-ligand. The solution started to generate white precipitate during the addition of hexamethyldisilazane. The reaction mixture was filtered to another 1000-mL 2- neck round bottom flask to remove all solids. The volatiles were evaporated from the filtrate and cesium fluoride (46.00 g, 302.85 mmol) and THF (300 mL) were added to the resulting residue. The flask was connected to a Schlenk line and methanol (300 mL) was added to the flask via cannula. The resulting mixture was stirred at room temperature overnight. Solvents were removed under reduced pressure and the resulting residue was dissolved with dichloromethane (800 mL). The mixture was filtered through a Celite-lined sintered glass funnel and the filter cake was washed with additional dichloromethane (3 x 30 mL). Volatiles from the filtrate were removed under reduced pressure to give a white powder (97.26 g, 99.2% yield). NMR (CD2Cl2, δ, ppm),1H: 7.70 (d, J = 7.9 Hz, 2H), 7.49 (t, J = 8.8 Hz, 1H), 7.39 (dd, J = 8.1, 1.8 Hz, 2H), 7.28-7.20 (m, 3H), 7.13 (tt, J = 7.6, 1.4 Hz, 1H), 6.40 (ddd, J = 7.9, 3.2, 1.2 Hz, 1H), 2.55 (m, 2H), 1.35 (q, J = 8.0 Hz, 6H), 1.28- 1.18 (m, 24H), 0.08 (b, 1H).31P{1H}: 44.71 (s). Complex 1 In a glove box, dispersed in toluene (~100 mL) in a 200-mL Schlenk flask. nBuLi (26.3 mL, 42.03 mmol) was added slowly over 30 minutes during which time the reaction became an orange-red slurry which was stirred for 2 h. The flask was taken to a fume hood and connected to a Schlenk line and then cooled to 0℃. TiCl2(NMe2)2 (4.24 g, 20.5 mmol) dissolved in toluene (100 mL, 0℃) and cooled to 0℃ was added slowly to the orange-red slurry, and the reaction was allowed to slowly warm to ambient temperature overnight. The mixture was filtered through a sintered glass funnel into a 500-mL Kontes flask, and the residue washed with toluene (3 x 10 mL). Silicon tetrachloride (13.93 g, 82 mmol) was added to the combined filtrate, the headspace of the vessel was evacuated, and the mixture heated at 60℃ for 5 h, and then allowed to cool to ambient temperature overnight. The flask was transferred to a glove box and the mixture filtered through a sintered glass funnel. The solids were washed with toluene (2 x 10 mL) and pentane (3 x 10 mL), and then dried under vacuum to give dark-red solids (8.2 g, 66.4% yield). NMR (CD2Cl2, δ, ppm),1H: 7.95 (dd, J = 8.9, 0.8 Hz, 2H), 7.80-7.64 (m, 4H), 7.59 (dd, J = 9.0, 1.8 Hz, 2H), 6.92 (m, 2H), 2.34 (m, 2H), 1.23 (s, 18H), 1.21 (m, 6H), 1.17 (m, 6H).31P{1H}: 33.0 (s). Complex 2 Complex 1 (2.5 g, bromide (5.4 mL, 16.2mmol, 3 M in Et2O) were combined in toluene (150 mL) and the mixture was stirred at ambient temperature overnight. All volatiles were removed, and the residue was completely dried under vacuum over 3 hours. The product was extracted with toluene ( 3× 50 mL) and filtered through a pad of Celite. The combined filtrate was reduced to ca.20 mL and layered with heptane (20 mL) and cooled to -35^C to precipitate the product as a brown solid (1.5 g, 64% yield). NMR (CD2Cl2, δ, ppm),1H: 8.12 (dd, J = 8.9 and 0.8 Hz, 2H), 7.62-7.52 (m, 3H), 7.49 (m, 1H), 7.43 (dd, J = 8.8 and 1.7 Hz, 2H), 6.72 (m, 2H), 2.29 (m, 2H), 1.21 (m, 6H), 1.19 (s, 18H), 1.11 (dd, J = 16.3 and 7.1 Hz, 6H), -0.95 (s, 6H, TiCH3).31P{1H}: 24.5. 4,4’-Di-tert-Butylbiphenyl Biphenyl 2-L flask with a stir bar in a glove box. Dichloromethane (450 mL), previously dried over activated 13X molecular Sieves, was transferred into the reaction flask. The flask was taken to a fume hood and connected to a high purity nitrogen source on a Schlenk line. A flask containing sodium hydroxide solution was connected to one of the necks of the flask. Tert-butyl chloride was added to the stirred solution at a controlled rate, over 2.5 hours, with a slow stream of nitrogen so that the HCl by-product was effectively transferred from the reaction flask and neutralized by the NaOH solution. The reaction mixture was stirred ~18 h during which time the mixture became dark brown. The mixture was washed with water in a separatory funnel and the dichloromethane fraction was separated and treated with anhydrous MgSO4, and then filtered through a Celite-lined sintered glass funnel into a 1-L round bottomed flask and the dichloromethane solvent was removed under reduced pressure on a rotary evaporator to give a solid (266 g, 100% yield). NMR (CDCl3, ^, ppm),1H: 7.61-7.54 (m, 4H), 7.52-7.46 (m, 4H), 1.41 (s, 18H). 2,2’-Dibromo-4,4’-Di-tert-Butylbiphenyl For a reference see Liu, Feng; et al., Tetrahedron Letters 2016, 57(37), 4157-4161. Dichloromethane (400 mL) was added to 4,4’-di-tert-butylbiphenyl (242.0 g, 0.908 mol) and iron powder (1.0 g, 2 mol%) in a two necked 1-L flask. A 1-L flask containing NaOH solution was connected to the reaction flask. Bromine (100 mL, 310.28 g, 1.94 mol) was added to the 1-L flask through a dropping funnel at room temperature over 4 hours and the generated HBr was neutralized by a NaOH solution. The mixture was stirred overnight, and saturated aqueous sodium bisulfite solution was added until the dark-coloured solution became almost colourless. The mixture was transferred to a separatory funnel and the organic layer separated and then dried with anhydrous MgSO4. The mixture was filtered through a Celite-lined sintered glass funnel and the filtrate evaporated to dryness. The crude material was washed with acetonitrile (4 x 230 mL) and then dried under vacuum to give a white solid (174 g, 45% yield). NMR (CDCl3, ^, ppm),1H: 7.66 (d, J = 2.0 Hz, 2H), 3.78 (dd, J = 8.0 Hz, J = 1.81 Hz, 2H), 7.18 (d, J = 8.0 Hz, 2H), 1.37 (s, 18H). Compound 5 To 2-fluorobenzoic acid in THF (40 mL) in a 200-mL Kontes flask was added benzyl potassium in THF (~30 mL) to form a slurry. tBu2PH (4.26 g, 29.18 mmol) in THF (20 mL) was added to the slurry. In a separate 100- mL hypovial, benzyl potassium (3.8 g, 29.18 mmol) in THF (30 mL) was added to t-Bu2PH (4.26 g, 29.18 mmol) and the mixture stirred for 1 h. This mixture was added to the Kontes flask and the resulting mixture was heated to 75℃ for 3 days. The mixture was allowed to cool to ambient temperature and then trifluoroacetic acid (3.33 g, 29.18 mmol) was added slowly. The volatiles from the resulting dark orange reaction mixture were removed under reduced pressure and the residue was treated with dichloromethane and water. The dichloromethane solution was separated and then treated with anhydrous MgSO4, filtered and the resulting filtrate was evaporated to dryness, washed with cold pentane (3 x 10 mL at -20℃) and dried under vacuum to give a pale yellow solid (5.82 g, 75% yield). NMR (CDCl3, ^, ppm),1H: 8.19-8.14 (m, 1H), 7.78-7.59 (m, 3H), 5.13 (d, J=257.8 Hz, 1H), 1.31 solution (~0.2 mL) was evaporated to dryness and analyzed by NMR to confirm complete consumption of the benzoic acid. NMR (CD2Cl2, ^, ppm),1H: 8.35-8.19 (m, 2H), 7.98-7.89 (m, 2H), 6.08 (d, J = 602.6 Hz, 1H), 4.08 (s, 3H), 1.51 (d, J = 19.2 Hz, 18H).31P{1H}: 69.1 (s). Triethylamine (3.5 g, 34.6 mmol) was added dropwise to the reaction mixture and the resulting solution was stirred for 2 hours at ambient temperature. Volatiles were removed under reduced pressure and the oily residue was extracted with pentane (3 x 40 mL) and the combined pentane extracts were evacuated to dryness to give a light yellow solid (5.318 g, 85%). NMR (toluene-d8, ^, ppm),1H: 7.72-7.67 (m, 1H), 7.27-7.21 (m, 1H), 7.07-7.95 (m, 2H), 3.63 (s, 3H), 1.16 (d, J = 11.7 Hz, 18H).31P{1H}: 25.59 (s). Compound 7 (2-Bromophenyl) mmol) was added to CuI (0.190 g, 1.00 mmol) and LiBr g, heptane (ca.20 mL). Tert- butylmagnesium chloride (10.0 mL, 2 M Et2O, 20.0 mmol) was added to the above mixture over ca.10 minutes. The mixture was stirred overnight at ambient temperature. The volatiles were removed under reduced pressure to give a white solid, which was extracted with pentane (3 x 10 mL) and filtered to give an orange filtrate. The volatiles were removed under reduced pressure to give an orange oil. The oil was extracted with heptane (3 x 10 mL) and filtered through a sintered-glass funnel to give a clear orange filtrate and a white residue on the sintered glass funnel. The heptane was removed from the filtrate to give an orange oil (2.206 g, 90% purity, 73% yield). NMR (toluene-d8, δ, ppm),1H: 7.62 (dd, 1H, ArH), 7.47 (dd, 1H, ArH), 6.91 (td, 1H, ArH), 6.72 (m, 1H, ArH), 1.13 (d, 18H, tBu).31P{1H}: 32.12 (s). Compound 8 n-BuLi in hexane was added slowly at room temperature to a solution of the 2,2’-dibromo-4,4’-di-tert-butylbiphenyl (2.229 g, 5.254 mmol) in a mixture of Et2O and THF (30 mL, Et2O:THF = 19:2). The reaction mixture was stirred for 30 minutes and then the volatiles were removed under reduced pressure. The resulting solid was re-dissolved in THF (25 mL), cooled to -35°C in a glove box freezer for 30 minutes and then it was added to a cold (-35°C) solution of Compound 6 (1.473 g, 5.254 mmol) in THF (20 mL). The reaction was allowed to warm to ambient temperature and stirred at room temperature for 1 hour and during which time a precipitate formed. The slurry was stirred over the weekend. A small amount of the slurry was pipetted into a vial while the bulk of the slurry was vigorously stirred. The small sample was pumped to dryness and the solid was re-dissolved in THF-d8(1.5 mL). LiOMe was filtered off and the filtrate was collected in an NMR tube.31P NMR showed the presence of three compounds with chemicals shifts at 16.9 ppm (15.9%), 15.6 ppm (82.2%) and 25.7 ppm (1.9%), which is unreacted Compound 6. The bulk of the reaction mixture was pumped to dryness and washed with pentane to remove unreacted Compound 6. To the white solid remaining was added ca.40 mL of degassed Et2O and ca.10 mL of water. The mixture was vigorously mixed, and the organic ether layer was separated from the aqueous layer. The aqueous layer was extracted with additional Et2O (3 × 10 mL) and the ether extracts combined. The combined extracts were dried with anhydrous MgSO4, filtered, and the MgSO4 washed with Et2O (3 × 30 mL) and filtered. The volatiles from the combined filtrate were removed under reduced pressure give a white crystalline solid (2.51 g, 93% yield). NMR (CD2Cl2, ^, ppm),1H: 8.12 (d, J = 18.4 Hz, 1H), 7.77 (dd, J = 7.9, J = 3.8, 1H), 7.57 (d, J = 7.8, 2H), 7.36 (dd, J = 7.9 Hz, J = 1.7 Hz, 2H), 7.25 (d, J = 1.4 Hz, 2H), 7.13 (t, J = 7.6 Hz, 1H), 6.97 (t, J = 7.8, 1H), 6.47 (dd, J = 8.4 Hz, J = 4.4 Hz, 1H), 1.44 (d, J = 12.7 Hz, 18H), 1.25 (s, 18H).31P{1H}: 12.7(s). Compound 9 METHOD A: A g) and glacial acetic acid solution (25 mL) was degassed and added to Compound 8 (0.704 g, 1.367 mmol) in a 50- mL Schlenk flask. The mixture was stirred at 70℃ for 36 hours and volatiles were removed by distillation under partial vacuum. The remaining solid was dried under vacuum and the solid was dissolved in dichloromethane (30 mL). Triethylamine (0.67 g) was added, and the mixture was stirred for 1.5 hours. The dichloromethane was removed, and the product was extracted with pentane (2 x 40 mL) and the pentane evaporated to dryness to give an off- white solid (0.6 g, 88.0%). NMR (CD2Cl2, ^, ppm),1H: 7.91(d, J = 7.8 Hz, 1H), 7.70 (d, J = 8.0 Hz, 2H), 7.39 (dd, J = 8.0, J = 1.83 Hz, 2H), 7.25 (s, 2H), 7.20 (td, J = 7.36 Hz, J = 1.43 Hz, 1H), 7.06 (t, J = 7.22, 1H), 6.75 (d, J = 14.65 Hz, 1H), 6.35 (ddd, J = 8.0 Hz, J = 4.37 Hz, J = 1.40 Hz, 1H), 1.39 (d, J = 12.02 Hz, 18H), 1.24 (s, 18H).31P{1H}: 16.3 (s). METHOD B: To Compound 7 (0.602 g, 2.0 mmol) in a pentane / THF mixture (97 / 3, 30 mL) in a 50 mL hypo-vial was added nBuLi (1.6M, 1.27 ml, 2.04 mmol). The resulting slurry was stirred for 20 minutes, and then 2,7-di-tert-butyl-9H-fluoren-9-one (0.585 g, 2.0 mmol) was added as solid. The light orange solution was stirred for 1 h at ambient temperature after which ~10 mL of the solvents were removed under reduced pressure and then THF (20 mL) was added. TiCl4(THF)2 (0.134 g, 0.4 mmol) in THF (10 mL) followed by LiAlH4(0.380 g, 10.0 mmol) in THF (10 ml) were also added to the reaction mixture, which was stirred at ambient temperature for 20 minutes and then heated at 60℃ overnight. The reaction was allowed to cool to ambient temperature, and methanol (3 mL), previously dried over sodium, was added dropwise to consume the un-reacted LiAlH4. The volatiles were removed under reduced pressure to give a grey solid, which was extracted with hot heptane (3 x 20 mL). The combined heptane extracts were evaporated to dryness to afford glittering white crystals which was washed with degassed methanol (3 x 4 mL) and then dried under vacuum to give a white glittering solid (0.912 g, 91% yield). NMR (CD2Cl2, ^, ppm),1H: 7.91(d, J = 7.8 Hz, 1H), 7.70 (d, J = 8.0 Hz, 2H), 7.39 (dd, J = 8.0, J = 1.83 Hz, 2H), 7.25 (s, 2H), 7.20 (td, J = 7.36 Hz, J = 1.43 Hz, 1H), 7.06 (t, J = 7.22, 1H), 6.75 (d, J = 14.65 Hz, 1H), 6.35 (ddd, J = 8.0 Hz, J = 4.37 Hz, J = 1.40 Hz, 1H), 1.39 (d, J = 12.02 Hz, 18H), 1.24 (s, 18H).31P{1H}: 16.3 (s). Compound 10 METHOD A: hexachloroethane (0.956 g, 4.038 mmol) were dissolved in dichloromethane (90 mL) in a 250-mL Kontes flask fitted with a stir bar. The mixture was stirred for 15 minutes and then the Kontes flask was attached to an ammonia gas delivery line and cooled to 0℃ in an ice / water bath. The delivery line and the headspace of the Kontes flask were evacuated and then charged with ammonia gas (5 psig). The mixture was stirred for 20 minutes during which time the pressure decreased to 2 psig and white precipitate formed. The reaction mixture was isolated from the ammonia supply and allowed to warm to ambient temperature overnight, and the pressure increased to 14 psig during this time. Unreacted ammonia was vented from the reaction flask and the slurry was filtered and the filter cake rinsed with dichloromethane (3 x 20 mL) and filtered. THF (~40 mL) was added to the white solid and then nBuLi (0.87 mL, 1.6 M in hexanes, 1.4 mmol) was added dropwise to the slurry until the colorless mixture became red and the resulting solution stirred for 30 minutes. MeOH (1 mL) was added, and the mixture stirred for 20 minutes. The volatiles were removed under reduced pressure and the resulting solid was extracted with toluene (2 x 10 mL), filtered, and then evacuated to dryness. The solid was washed with cold pentane (40 mL at -35°C) and dried under vacuum to give pure product (1.80 g, 87% yield). NMR (toluene-d8, ^, ppm),1H: 7.73 (d, J = 7.70 Hz, 2H), 7.56 (d, J = 1.63 Hz, 2H), 7.52 (t, J = 9.08 Hz, 1H), 7.35 (dd, J = 8.04, J = 1.86, 2H), 6.82-6.76 (m, 1H), 6.68-6.61 (m, 1H), 6.56-6.50 (m, 1H), 1.37 (d, J = 13.07, 18H), 1.25 (s, 18H).31P{1H}: 48.08(s). METHOD B: To Compound 9 (2.014 g, 4.038 mmol) in dichloromethane (~30 mL) at 0°C in a 200 mL of thick-walled Kontes flask was added hexachloroethane (0.956 g, 4.039 mmol) in dichloromethane (10 mL). The reaction mixture was stirred for ~10 minutes, the head space of the Kontes flask was evacuated and then NH3gas (5 psig) was added. The resulting white slurry mixture was stirred for 1 h at 0°C and at ambient temperature for 1 h. The excess amount of ammonia was vented to a bubbler. Lithium isopropoxide (0.534 g, 8.08 mmol) in THF, prepared by treating absolute isopropanol (0.7 mL, 9.2 mmol) in THF (30 mL), cooled at 0°C, with nBuLi (5.05 mL, 1.6 M in hexanes, 8.08 mmol), was added to the above reaction mixture. The slurry was allowed to warm to ambient temperature. The volatiles were removed under reduced pressure and the resulting solid was extracted with dichloromethane (4 x 7 mL) and filtered through a pad of Celite on a sintered-glass funnel. The combined filtrate was pumped to dryness to give a white solid (2.11 g, 100% yield). NMR (toluene-d8, ^, ppm),1H: 7.73 (d, J = 7.70 Hz, 2H), 7.56 (d, J = 1.63 Hz, 2H), 7.52 (t, J = 9.08 Hz, 1H), 7.35 (dd, J = 8.04, J = 1.86, 2H), 6.82- 6.76 (m, 1H), 6.68-6.61 (m, 1H), 6.56-6.50 (m, 1H), 1.37 (d, J = 13.07, 18H), 1.25 (s, 18H). 31P{1H}: 48.08(s). Complex 3 To Compound 10 mL) in a 100-mL hypovial cooled at -35°C was added . mixture became dark red and was stirred for 3 h. and then cooled at -35℃. This solution was added to a slurry of TiCl4(THF)2 (1.17 g, 3.504 mmol) in toluene (35 mL) also cooled at -35℃. The mixture allowed to warm to ambient temperature and stirred overnight. The slurry was filtered through a sintered glass funnel and the red solid collected was extracted with dichloromethane (4 x 3 mL) until it became white. The combined extract was concentrated to ca.15 mL then cooled at -35℃ overnight. The precipitated solids was filtered, washed with cold toluene / pentane mixture (70:30, 3 x 15 mL), then with pentane (3 x 10 mL) and dried under vacuum to give a red solid (1.5 g, 68% yield). NMR (CD2Cl2, ^, ppm),1H: 7.97-7.91 (multiplet and overlapping doublet, 3H), 7.80-7.64 (m, 3H), 7.56 (dd, J = 8.88 Hz, mL Methylmagnesium bromide (1.2 mL, 3.0 M in diethyl ether) was added dropwise. The solution was stirred for 70 minutes and turned from wine red color to light yellow. The volatiles were removed under reduced pressure and the residue was mixed with toluene (30 mL) for a few minutes, and then pumped to dryness again. The residue was extracted with toluene (25 mL), filtered and the filtrate was evaporated to dryness to give a yellow solid (0.612 g, 86% yield). NMR (toluene-d8, ^, ppm),1H: 8.15 (d, J = 8.83, 2H), 7.52 (t, J = 8.10 Hz, 1H), 7.41 (dd, J = 8.87 Hz, J = 1.72 Hz, 2H), 7.23-7.17 (m, 1H), 7.08-6.97 (m, 2H), 6.87 (s, 2H), 1.22 (s, 18H), 1.20 (d, J = 14.7 Hz, 18H), -0.31 (s, 6H).31P{1H}: 24.68 (s). Compound 11 9H-fluorene 2,5-diol (20.539 g, 140 mmol) were added to a hot 250 mL 2-neck round bottom flask fitted with a stir bar. The flask was connected to a Schlenk line, and the contents evacuated and re-filled (3x) with nitrogen to remove moisture and oxygen. Once the flask was at ambient temperature, dichloromethane (90 mL) was added to the flask via a cannula, and the mixture cooled to −15°C in an ice-salt bath. A solution of AlCl3 (40.112 g, 301 mmol) in nitromethane (80 mL) was added dropwise to the mixture over 2 h. The mixture darkened to form a black mixture. After 3 h, the ice-bath was replaced with a water bath and the mixture was stirred overnight. The thick, dark mixture was slowly poured into ice-cold water (200 mL), which caused an immediate colour change from black to colourless and the formation of a white precipitate. The mixture was extracted with diethyl ether (3 x 200 mL), and the combined extracts washed with saturated NaHCO3 solution (200 mL) and then dried over MgSO4and filtered. The volatiles were removed under reduced pressure to give Compound 11 as an off-white solid (22.129 g, 95% yield). NMR (CDCl3, ^, ppm),1H: 7.66 (s, 2H), 7.43 (s, 2H), 3.76 (s, 2H), 1.72 (s, 8H), 1.38 (s, 12H), 1.32 (s, 12H). Compound 12 To Compound 11 mL) was added BnNMe3OH (4 mL, 40% aq, 9.4 , to form. The mixture was heated to 45°C and then hydrogen peroxide (16 mL, 30% aq, 141 mmol) was added dropwise of over 1.5 h. The resulting mixture was allowed to cool to ambient temperature with stirring overnight. Water (200 mL) was added, which resulted in the precipitation of a light yellow solid. The solid was collected by filtration and rinsed with water (3 x 50 mL), dried under a flow of dry nitrogen over the weekend, and then under reduced pressure to afford a yellow, free flowing powder (17.2 g, 91% yield). NMR (CDCl3, ^, ppm),1H: 7.60 solution was stirred for 30 minutes at ambient temperature. The volatiles were removed under reduced pressure to give a tan coloured solid. THF (40 mL) was added to dissolve the solid and the solution was cooled at -35℃ in a glove box freezer for 20 minutes. This solution was added to a cold (-35℃) solution of Compound 6 (1.409 g, 5.026 mmol) in THF (20 mL). The mixture was allowed to warm to ambient temperature and stirred overnight. The mixture was filtered, and the solid residue was washed with warm THF (150 mL at 50℃) and filtered. The combined filtrate was evaporated to dryness and the solid was washed with pentane and dried under vacuum to give a white solid (2.054 g, 65% yield). NMR (THF-d8, ^, ppm),1H: 9.06-8.97 (m, 1H), 7.50 (s, 2H), 7.41 (d, J = 7.51 Hz, 1H), 7.24 (t, J = 7.81 Hz, 1H), 6.99 (t, J = 7.21 Hz, 1H), 6.88 (s, 2H), 1.71-1.59 (m, 8H), 1.37 (s, 6H), 1.33 (s, 6H), 1.25 (s, 6H), 1.06 (s, 6H), 0.62 (d, J = 11.09 Hz, 18H).31P{1H}: 14.5 (s). METHOD B: Compound 7 (0.69 g, 2.53 mmol) was dissolved in heptane (ca. 20 mL) and THF (0.193 g, 2.68 mmol). nBuLi (1.6 mL, 1.6 M in hexanes, 2.56 mmol) was added which caused a light brown colouration, followed by formation of precipitate. The mixture was stirred for 10 minutes and then Compound 12 (1.011 g, 2.53 mmol) was added as a powder. A brown orange colour developed and additional precipitate formed. The mixture was stirred at room temperature for 2 h. The mixture was placed under dynamic vacuum to partially remove volatiles and cool the solution at -35℃. The precipitated solids were collected by filtration on a sintered glass funnel and washed with pentane (3 x 10 mL) and dried under dynamic vacuum to give a white solid (1.284 g, 84% yield). NMR (THF- d8, δ, ppm),1H: 9.01 (dd, 1H, PhH), 7.50 (s, 2H, ArH), 7.41 (d, 1H, PhH), 7.24 (t, 1H, PhH), 7.00 (td, 1H, PhH), 6.88 (s, 2H, ArH), 1.66 (broad multiplet, 8H, -CH2), 1.37 (s, 6H, - CH3), 1.33 (s, 6H, -CH3), 1.25 (s, 6H, -CH3), 1.06 (s, 6H, -CH3), 0.618 (d, 18H, tBu).31P{1H}: 12.64 (s). Compound 14 Compound 13 (~40 mL) in a 250 mL Schlenk flask in a glove box. TiCl4(THF)2(1.67 g, 5 mmol) in THF (20 mL) followed by LiAlH4 (1.5 g, 40 mmol) in THF (30 mL) were added to the above stirred solution. The mixture was heated to 60℃ for 72 h during which a brown-orange solution formed. Degassed MeOH (25 mL) was added to the mixture and the volatiles removed under reduced pressure. The resulting solid was extracted with pentane (4 x 25 mL), and the greenish-brown combined pentane solution was filtered through a 1” high and 1” diameter alumina column, and the column rinsed with additional pentane (30 mL). The combined filtrate was pumped to dryness to give a white solid (1.638 g, 54% yield). NMR (CD2Cl2, ^, ppm),1H: 7.89 (d, J = 7.92 Hz, 1H), 7.70 (s, 2H), 7.19-7.15 (m, 1H), 7.12 (s, 2H), 7.07 (t, J = 7.37 Hz, 1H), 6.65 (d, J = 14.75 Hz, 1H), 6.38 (ddd, J = 8.0 Hz, J = 4.55 Hz, J = 1.55 Hz, 1H), 1.76-1.53 (m, 8H), 1.40 (s, 6H) overlaps with the t-Bu2P doublet at 1.38 ppm, 1.38 (d, J = 11.95 Hz, 18H), 1.36 (s, 6H) overlaps with the t-Bu2P doublet at 1.38 ppm, 1.20 (s, 6H), 1.08 (s, 6H).31P{1H}: 16.34 (s). Compound 15 Compound 14 (0.487 g, 2.059 mmol) were dissolved in dichloromethane (30 mL) in a 500-mL Kontes flask fitted with a stir bar. The mixture was stirred for 15 minutes and then the Kontes flask was attached to an ammonia gas delivery line and cooled to 0℃ in an ice / water bath. The delivery line and the headspace of the Kontes flask were evacuated and then charged with ammonia gas (4 psig). The mixture was stirred for 20 minutes during which time the pressure decreased to 2 psig and white precipitate formed. The reaction mixture was isolated from the ammonia supply and allowed to warm to ambient temperature and unreacted ammonia was vented from the reaction flask. The Kontes flask was closed, and the reaction was stirred overnight. The pressure was released completely, and the dichloromethane solution was filtered. The white solid was rinsed with dichloromethane (3 x ~7 mL). The filtrate was pumped to dryness to give a sticky white solid. THF (40 mL) was added to the solid to make a slurry and Buli (0.73 mL, 1.6 M in hexanes, 1.2 mmol) was added dropwise to the slurry until the colorless mixture became red and the resulting solution stirred for ~10 minutes. Absolute MeOH (~0.25 mL) was added to react with the excess amount of BuLi. The volatiles were removed under reduced pressure and the resulting solid was extracted with toluene (2 mL) and DCM (20 mL). The combined extracts were evaporated to dryness and the residue re- dissolved in toluene (~30 mL) and was pumped to dryness to give a white solid (1.375 g, 93% yield). NMR (CD2Cl2, ^, ppm),1H: 8.45-8.06 (br s,1H), 7.74 (t, J = 8.83 Hz, 1H), 7.70 (s, 2H), 7.27-7.12 (m, 4H), 7.11 (s, 2H), 6.41 (m, 1H), 2.34 (s, 1.8), 1.74-1.62 (m, 8H), 1.48 (d, J = 13.33 Hz, 18H), 1.40(s, 6H), 1.36 (s, 6H), 1.23 (s, 6H), 1.09 (s, 6H).31P{1H}: 49.7 (s). Complex 5 Compound 15 dissolved in toluene (20 mL) and nBuLi (2.45 mL, 1.6 M in hexanes, 3.92 mmol) was added slowly. The slurry was stirred for 2 h at ambient temperature and was cooled at -35℃ in a glove box freezer for 5 minutes. TiCl4(THF)2(0.624 g, 1.867 mmol) in toluene (20 mL) was also cooled at -35℃ in the freezer for 5 minutes. The dilithium salt was added quickly to TiCl4(THF)2 solution and the mixture allowed to warm to ambient temperature overnight. The volatiles were removed under reduced pressure and the solid was extracted with hot heptane (60 ml, 60℃) and filtered through a sintered glass funnel. The filter cake was washed with dichloromethane (~15 mL). The combined filtrate was concentrated (to remove dichloromethane) and a brown solid precipitated. The brown solid was removed by filtration and the filtrate was cooled at -35℃ in a glove box freezer for 72 h. A red crystalline solid deposited, which was collected by filtration, washed with pentane (3 x 5 mL) and dried under vacuum (0.7 g, 51% yield). NMR (CD2Cl2, ^, ppm),1H: 8.00 (s, 2H), 7.93 (t, J = 8.65 Hz, 1H), 7.77-7.60 (m, 3H), 6.88 (s, 2H), 1.79-1.64 (m, 8H), 1.51 (s, 6H), 1.43 (s, 6H), 1.34 (d, J = 15.33 Hz, 18H), 1.18 (s, 6H), 1.05 (s, 6H).31P{1H}: 34.8 (s). Solution Phase Polymerization: Continuous Ethylene / 1-Octene Copolymerization Solution phase polymerizations were conducted on a continuous polymerization unit (CPU) using cyclohexane as the solvent and a stirred 70 mL reactor operated between 190°C and 240°C. An upstream mixing reactor having a 20 mL volume was operated at 5°C lower than the polymerization reactor. The mixing reactor was used to pre-heat the ethylene, octene, and make-up solvent streams. Catalyst feeds such as an ortho-xylene or cyclohexane solutions of the organometallic complex (the pre-polymerization catalyst); the boron-based catalyst activators, (Ph3C)[B(C6F5)4] (TB) or di(hydrogenated tallow)methylammonium (‘Armeenium’) tetrakis(pentafluorophenyl)borate; the aluminum- based co-catalysts, alkylaluminoxane (MMAO-7) or diethylaluminum ethoxide (DEAL-E); the hindered phenol modifier, 2,6-di-tert-butyl-4-ethylphenol (BHEB); and additional make-up cyclohexane solvent flow were either combined in-line as desired or added directly to the reactor in a continuous process. The total solution flow for all feeds into the reactor was maintained at 27 mL / min. Ethylene / 1-octene copolymers were made using 1-octene / ethylene weight ratios as stated in Table 1, or alternatively ethylene homopolymers were made by turning off the flow of 1-octene. The ethylene was fed at different rates depending on the reactor temperature: 3.50 g / min at 190°C, 3.80 g / min at 200°C, 4.10 g / min at 210°C, 4.48 g / min at 220°C, 4.77 g / min at 230°C, 4.93 g / min at 240°C. The CPU system operated at a pressure of 10.5 MPa. The solvent, monomer, and comonomer streams were purified by purification trains before being fed to the reactor. The polymerization activity, kp (expressed in mM-1×min-1), is defined as: ^^ 1 1 ^^୮ ൌ ൬^^^ ൬ ൬^ where Q is ethylene NIR detector), [M] is catalyst concentration in the reactor (M = Ti; concentration in mM), and HUT is hold-up time in the reactor (a value of 2.6 min was used). Copolymer samples were collected with a target of 90 ±1% ethylene conversion (Q), dried in a vacuum oven, and then ground and homogenized prior to analysis. In cases where the 90% target was not able to be met due to low catalyst activity, no polymer sample was taken. Polymerization conditions and results are provided in Tables 1 and 2.

[0006] TABLE 1 Continuous Ethylene / 1-Octene Copolymerization Conditions – 190 to 240°C Experiments Poly. Catalyst Reactor Ethylene B / Ti Al / Ti BHEB / Al 1-Octene / Run No. Complex Temp. Flow (Molar (Molar (Molar Ethylene No. (°C) (g / min) Ratio) Ratio) Ratio) Ratio (wt / wt) 1 Complex 2 190 3.5 1.4 5 0.6 0.3 2 Complex 2 200 3.8 1.4 5 0.6 0.3 3 Complex 2 210 4.10 1.4 5 0.6 0.3 4 Complex 2 220 4.48 1.4 5 0.6 0.0 5 Complex 2 220 4.48 1.4 5 0.6 0.15 6 Complex 2 220 4.48 1.4 5 0.6 0.3 7 Complex 2 220 4.48 1.4 5 0.6 0.5 8 Complex 2 230 4.77 1.4 5 0.6 0.3 9 Complex 2 240 4.93 1.4 5 0.6 0.3 10 Complex 3 220 4.48 1.60 20 1.36 0.30 11 Complex 3 220 4.48 1.60 20 1.36 0.50 12 Complex 3 220 4.48 1.60 20 1.34 0.15 13 Complex 3 230 4.77 1.60 20 1.36 0.30 14 Complex 3 240 4.93 1.60 20 1.35 0.30 15 Complex 3 220 4.48 1.80 40 1.50 0.30 16* Complex 3 220 4.48 1.80 40 1.50 0.30 17* Complex 3 220 4.48 1.60 60 1.35 0.30 18* Complex 3 230 4.77 1.60 60 1.35 0.30 19* Complex 3 240 4.93 1.60 65 1.35 0.30 20** Complex 3 220 4.48 1.80 40 1.35 0.30 21** Complex 3 220 4.48 1.80 40 0.00 0.30 22** Complex 3 220 4.48 1.60 40 0.00 0.30 23** Complex 3 220 4.48 1.40 40 0.00 0.30 24** Complex 3 220 4.48 1.20 40 0.00 0.30 25 Complex 4 190 3.50 1.20 5.0 0.6 0.3 26 Complex 4 200 3.80 1.20 5.0 0.6 0.3 27 Complex 4 210 4.10 1.20 5.0 0.6 0.3 28 Complex 4 220 4.48 1.20 5.0 0.6 0.15 29 Complex 4 220 4.48 1.20 5.0 0.6 0.3 30 Complex 4 220 4.48 1.20 5.0 0.0 0.3 31 Complex 4 220 4.48 1.20 5.0 0.6 0.5 32 Complex 4 230 4.77 1.40 10.0 0.6 0.3 33 Complex 4 230 4.77 1.40 10.0 0.6 0.0 34 Complex 4 240 4.93 1.40 10.0 0.6 0.3 35 Complex 4 240 4.93 1.40 10.0 0.6 0.0 36 Complex 5 220 4.48 1.60 25.00 1.4 0.30 37 Complex 5 220 4.48 1.60 25.00 1.4 0.50 38 Complex 5 220 4.48 1.60 25.00 1.4 0.15 39 Complex 5 230 4.77 1.60 25.00 1.4 0.30 40 Complex 5 240 4.93 1.60 25.00 1.4 0.30 41* Complex 5 220 4.48 1.80 30.0 1.4 0.30 42* Complex 5 230 4.77 1.80 30.0 1.4 0.30 43* Complex 5 240 4.93 1.80 30.0 1.4 0.30 * AB activator; ** AB activator and DEAL-E co-catalyst. TABLE 2 Continuous Ethylene / 1-Octene Copolymerization Results – 190 to 240°C Experiments Poly. [Ti] Ethylene kpFTIR BrF FTIR BrF GPC-RI MnGPC-RI MwGPC-RI MzGPC-RI Run (µM) Conversion (mM-1(no. (Wt%) Mw / MnNo. (Q %) ^min-1) / 1000C) 1 0.51 89.43 6408 14.8 10.9 76880 159486 284784 2.07 2 0.69 89.85 4917 14.9 10.9 73109 133680 221215 1.83 3 1.17 90.66 3209 16 11.7 54527 106641 180321 1.96 4 4.44 89.65 752 2.3 1.8 76284 160031 293188 2.1 5 2.59 90.21 1371 8.8 6.7 55511 113404 190560 2.04 6 1.89 90.81 2018 16 11.7 46188 88020 142871 1.91 7 2.31 89.94 1490 24 16.8 35282 68625 110726 1.95 8 2.11 90.01 1646 15.5 11.3 37803 93265 168932 2.47 9 2.94 90.3 1219 16 11.7 35492 76193 131445 2.15 10 0.74 90.07 4,700 - - - - - - 11 0.74 89.78 4,552 - - - - - - 12 0.91 89.75 3,707 - - - - - - 13 1.02 89.59 3,247 - - - - - - 14 1.67 89.76 2,029 - - - - - - 15 0.78 89.77 4,352 - - - - - - 16* 0.78 89.56 4,254 - - - - - - 17* 0.76 90.26 4,731 - - - - - - 18* 1.06 90.15 3,344 - - - - - - 19* 1.39 89.65 2,406 - - - - - - 20** 1.67 89.60 1,994 - - - - - - 21** 1.02 89.92 3,366 - - - - - - 22** 1.02 89.75 3,304 - - - - - - 23** 1.02 90.00 3,396 - - - - - - 24** 1.02 90.00 3,396 - - - - - - 25 0.44 90.46 8,229 16.7 12.1 72000 168000 339000 2.33 26 0.5 89.64 6,725 16.1 11.7 66200 152000 294000 2.3 27 0.67 90.02 5,219 15.4 11.3 54500 129000 241000 2.37 28 1.16 90.43 3,154 10 7.6 53700 133000 255000 2.47 29 0.98 90.01 3,554 15.3 11.2 43100 108000 197000 2.5 30 1.07 90.43 3,417 15.5 11.4 41000 104000 185000 2.52 31 1.02 89.70 3,286 24.1 16.8 37900 87000 147000 2.3 32 1.60 89.74 2,109 15 11 35,100 90,400 156,000 2.58 33 4.67 89.74 723 - - 58500 157000 297000 2.69 34 2.22 89.73 1,517 16.1 11.7 29200 74700 127000 2.56 35 5.56 89.80 611 - - 55800 145000 268000 2.6 36 0.56 89.70 6,046 - - - - - - 37 0.61 90.05 5,712 - - - - - - 38 0.70 90.34 5,153 - - - - - - 39 0.78 90.48 4,713 - - - - - - 40 0.98 90.05 3,570 - - - - - - 41* 0.51 89.93 6,739 - - - - - - 42* 0.61 89.73 5,515 - - - - - - 43* 0.83 89.95 4,143 - - - - - - * AB activator; ** AB activator and DEAL-E co-catalyst. The data provided in Tables 1 and 2 show that the synthetic methods disclosed herein give rise to highly active single catalysts for the polymerization of ethylene with alpha-olefins such as 1-octene. Non-limiting embodiments of the present disclosure include the following: Embodiment 1. A method for making a trihydrocarbyl phosphine compound having the formula I, , the having the formula II, a Grignard reagent, RMgCl, then with ZnCl2 and then with the formula III, ; compound having the formula III with a Grignard reagent, R1MgCl in the presence of copper iodide, CuI and lithium bromide, LiBr to provide a compound having the formula IV, ; compound having the formula IV with an organolithium compound, R*Li and then with a compound having the formula V, provide a compound having the formula VI-OLi, nd he formula VI-OLi with LiAlH4in the presence of TiCl4 or TiCl4(THF)2 to provide the trihydrocarbyl phosphine compound having the formula I; wherein R is a C1-20 alkyl group; wherein R* is a C1-20 alkyl group; wherein R1is a primary alkyl group, or a secondary alkyl group, or a tertiary alkyl group; wherein R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; a fluorine atom; a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; wherein two adjacent groups of R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; wherein X is I or Br; and wherein X* is I or Br. Embodiment 2. The method of Embodiment 1 wherein R1is a secondary alkyl group or a tertiary alkyl group. Embodiment 3. The method of Embodiment 1 wherein R1is a tert-butyl group. Embodiment 4. The method of Embodiment 1 wherein R1is an iso-propyl group. Embodiment 5. The method of any one of Embodiments 1 to 4 wherein R7, R8, R9, and R10are each independently selected from the group consisting of a hydrogen atom; a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; and wherein two adjacent groups of R7, R8, R9, and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group. Embodiment 6. The method of any one of Embodiments 1 to 4 wherein R7, R8, R9, and R10are each independently selected from the group consisting of a hydrogen atom; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R7, R8, R9, and R10may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group. Embodiment 7. The method of any one of Embodiments 1 to 4 wherein R7, R8, R9, and R10are hydrogen. Embodiment 8. The method of any one of Embodiments 1 to 7 wherein R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; and wherein two adjacent groups of R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group. Embodiment 9. The method of any one of Embodiments 1 to 7 wherein R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; and wherein two adjacent groups of R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group. Embodiment 10. The method of any one of Embodiments 1 to 7 wherein each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is independently a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6- 20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group. Embodiment 11. The method of any one of Embodiments 1 to 7 wherein each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is independently a C1-20alkyl group. Embodiment 12. The method of any one of Embodiments 1 to 7 wherein each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is a tert-butyl group. Embodiment 13. The method of any one of Embodiments 1 to 7 wherein each of R11, R14, R15, and R18is a hydrogen atom and R12, R13, R16and R17are each independently a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; wherein two adjacent groups of R12, R13, R16and R17may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group. Embodiment 14. The method of any one of Embodiments 1 to 7 wherein each of R11, R14, R15, and R18is a hydrogen atom and R12, R13, R16and R17are each independently a C1-20 alkyl group. Embodiment 15. The method of any one of Embodiments 1 to 7 wherein each of R11, R14, R15, and R18is a hydrogen atom, and adjacent groups of R12and R13, and adjacent groups of R16and R17are: marks the point of attachment to adjacent fluorenyl group carbon atoms. Embodiment 16. The method of any one of Embodiments 1 to 15 wherein X is Br. Embodiment 17. The method of any one of Embodiments 1 to 16 wherein X* is Br. Embodiment 18. A method for making a pre-metallation compound having the formula PM-I-H, , the phosphine compound having the formula I , with an oxidant selected from the group consisting of Br2, Cl2, and Cl3C-CCl3; and then with ammonia, NH3; and optionally then with a base to provide the pre-metallation compound having the formula PM-I-H; wherein R1is a primary alkyl group, or a secondary alkyl group, or a tertiary alkyl group; wherein R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; a fluorine atom; a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group. Embodiment 19. The method of Embodiment 18 wherein R1is a secondary alkyl group or a tertiary alkyl group. Embodiment 20. The method of Embodiment 18 wherein R1is a tert-butyl group. Embodiment 21. The method of Embodiment 18 wherein R1is an iso-propyl group. Embodiment 22. The method of any one of Embodiments 18 to 21 wherein R7, R8, R9, and R10are each independently selected from the group consisting of a hydrogen atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; and wherein two adjacent groups of R7, R8, R9, and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group. Embodiment 23. The method of any one of Embodiments 18 to 21 wherein R7, R8, R9, and R10are each independently selected from the group consisting of a hydrogen atom; and a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group; and wherein two adjacent groups of R7, R8, R9, and R10may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group. Embodiment 24. The method of any one of Embodiments 18 to 21 wherein R7, R8, R9, and R10are hydrogen. Embodiment 25. The method of any one of Embodiments 18 to 24 wherein R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and wherein two adjacent groups of R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group. Embodiment 26. The method of any one of Embodiments 18 to 24 wherein R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; wherein two adjacent groups of R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, a C7-20 arylalkyloxy group. Embodiment 27. The method of any one of Embodiments 18 to 24 wherein each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is independently a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group. Embodiment 28. The method of any one of Embodiments 18 to 24 wherein each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is independently a C1-20alkyl group. Embodiment 29. The method of any one of Embodiments 18 to 24 wherein each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is a tert-butyl group. Embodiment 30. The method of any one of Embodiments 18 to 24 wherein each of R11, R14, R15, and R18is a hydrogen atom and R12, R13, R16and R17are each independently a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R12, R13, R16and R17may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, a C7-20arylalkyloxy group. Embodiment 31. The method of any one of Embodiments 18 to 24 wherein each of R11, R14, R15, and R18is a hydrogen atom and R12, R13, R16and R17are each independently a C1-20alkyl group. Embodiment 32. The method of any one of Embodiments 18 to 24 wherein each of R11, R14, R15, and R18is a hydrogen atom, and adjacent groups of R12and R13, and adjacent groups of R16and R17are: marks the point of attachment to adjacent fluorenyl group carbon atoms. INDUSTRIAL APPLICABILITY Synthetic methods to make trihydrocarbyl phosphines and phosphinimine pre- metallation compounds which may be used to make single site polymerization catalysts are provided. Such single site polymerization catalysts may be used to make polyolefins such as polyethylene at relatively high temperatures in solution phase polymerization processes

Claims

CLAIMS 1. A method for making a trihydrocarbyl phosphine compound having the formula I, , thehaving the formula II, a Grignard reagent, RMgCl, then with ZnCl2 and then with the formula III,;compound having the formula III with a Grignard reagent, R1MgCl in the presence of copper iodide, CuI and lithium bromide, LiBr to provide a compound having the formula IV, ;compound having the formula IV with an organolithium compound, R*Li and then with a compound having the formula V, provide a compound having the formula VI-OLi,nd the formula VI-OLi with LiAlH4 in the presence of TiCl4or TiCl4(THF)2to provide the trihydrocarbyl phosphine compound having the formula I; wherein R is a C1-20alkyl group; wherein R* is a C1-20 alkyl group; wherein R1is a primary alkyl group, or a secondary alkyl group, or a tertiary alkyl group; wherein R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; a fluorine atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; wherein X is I or Br; and wherein X* is I or Br.

2. The method of claim 1 wherein R1is a secondary alkyl group or a tertiary alkyl group.

3. The method of claim 1 wherein R1is a tert-butyl group.

4. The method of claim 1 wherein R1is an iso-propyl group.

5. The method of claim 1 wherein R7, R8, R9, and R10are each independently selected from the group consisting of a hydrogen atom; a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; and wherein two adjacent groups of R7, R8, R9, and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group.

6. The method of claim 1 wherein R7, R8, R9, and R10are each independently selected from the group consisting of a hydrogen atom; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R7, R8, R9, and R10may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group.

7. The method of claim 1 wherein R7, R8, R9, and R10are hydrogen.

8. The method of claim 1 wherein R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and wherein two adjacent groups of R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group.

9. The method of claim 1 wherein R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; and a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of afluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; and wherein two adjacent groups of R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group.

10. The method of claim 1 wherein each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is independently a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

11. The method of claim 1 wherein each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is independently a C1-20 alkyl group.

12. The method of claim 1 wherein each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is a tert-butyl group.

13. The method of claim 1 wherein each of R11, R14, R15, and R18is a hydrogen atom and R12, R13, R16and R17are each independently a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R12, R13, R16and R17may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group.

14. The method of claim 1 wherein each of R11, R14, R15, and R18is a hydrogen atom and R12, R13, R16and R17are each independently a C1-20alkyl group.

15. The method of claim 1 wherein each of R11, R14, R15, and R18is a hydrogen atom, and adjacent groups of R12and R13, and adjacent groups of R16and R17are: marks the point of attachment to adjacent fluorenyl group carbon16. The method of claim 1 wherein X is Br.

17. The method of claim 1 wherein X* is Br.

18. A method for making a pre-metallation compound having the formula PM-I-H, , the phosphine compound having theformula I , withconsisting of Br2, Cl2, and Cl3C-CCl3; and then with ammonia, NH3; and optionally then with a base to provide the pre-metallation compound having the formula PM-I-H; wherein R1is a primary alkyl group, or a secondary alkyl group, or a tertiary alkyl group;wherein R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; a fluorine atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group.

19. The method of claim 18 wherein R1is a secondary alkyl group or a tertiary alkyl group.

20. The method of claim 18 wherein R1is a tert-butyl group.

21. The method of claim 18 wherein R1is an iso-propyl group.

22. The method of claim 18 wherein R7, R8, R9, and R10are each independently selected from the group consisting of a hydrogen atom; a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group; anda heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and wherein two adjacent groups of R7, R8, R9, and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group.

23. The method of claim 18 wherein R7, R8, R9, and R10are each independently selected from the group consisting of a hydrogen atom; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; and wherein two adjacent groups of R7, R8, R9, and R10may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group.

24. The method of claim 18 wherein R7, R8, R9, and R10are hydrogen.

25. The method of claim 18 wherein R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and wherein two adjacent groups of R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group.

26. The method of claim 18 wherein R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of a hydrogen atom; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, and a C7-20 arylalkyloxy group; wherein two adjacent groups of R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20alkylaryloxy group, a C7-20 arylalkyloxy group.

27. The method of claim 18 wherein each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is independently a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20aryl group, a C6-20aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

28. The method of claim 18 wherein each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is independently a C1-20alkyl group.

29. The method of claim 18 wherein each of R11, R13, R14, R15, R16and R18is a hydrogen atom and each of R12and R17is a tert-butyl group.

30. The method of claim 18 wherein each of R11, R14, R15, and R18is a hydrogen atom and R12, R13, R16and R17are each independently a C1-30hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20alkylaryloxy group, and a C7-20arylalkyloxy group; wherein two adjacent groups of R12, R13, R16and R17may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a fluorine atom, a C1-20alkyl group, a C1-20alkoxy group, a C7-20alkylaryl group, a C7-20arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group.

31. The method of claim 18 wherein each of R11, R14, R15, and R18is a hydrogen atom and R12, R13, R16and R17are each independently a C1-20 alkyl group.

32. The method of claim 18 wherein each of R11, R14, R15, and R18is a hydrogen atom, and adjacent groups of R12and R13, and adjacent groups of R16and R17are:marks the point of attachment to adjacent fluorenyl group carbon atoms.

Images