WO2018125826A1 - Procédés d'oligomérisation d'éthylène - Google Patents

Procédés d'oligomérisation d'éthylène Download PDF

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WO2018125826A1
WO2018125826A1 PCT/US2017/068281 US2017068281W WO2018125826A1 WO 2018125826 A1 WO2018125826 A1 WO 2018125826A1 US 2017068281 W US2017068281 W US 2017068281W WO 2018125826 A1 WO2018125826 A1 WO 2018125826A1
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WIPO (PCT)
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group
metal salt
alternatively
phenanthroline
groups
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PCT/US2017/068281
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English (en)
Inventor
Steven M. BISCHOF
Brooke L. Small
Ryan W. Snell
Ron D. Knudsen
Eric J. Netemeyer
Orson L. Sydora
Jamie N. SUTHERLAND
Bruce E. Kreischer
William J. Fisher
Matthew F. MILNER
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Chevron Phillips Chemical Company Lp
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Priority claimed from US15/394,411 external-priority patent/US20180186708A1/en
Priority claimed from US15/394,317 external-priority patent/US10604457B2/en
Application filed by Chevron Phillips Chemical Company Lp filed Critical Chevron Phillips Chemical Company Lp
Priority to EP17832164.2A priority Critical patent/EP3562799B1/fr
Priority to CN201780080378.9A priority patent/CN110099884B/zh
Priority claimed from US15/852,623 external-priority patent/US10407360B2/en
Publication of WO2018125826A1 publication Critical patent/WO2018125826A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present disclosure relates to processes for producing alpha olefins. More particularly, the present disclosure relates to improved processes for oligomerizing ethylene.
  • Alpha olefins are important items of commerce. Their many applications include employment as intermediates in the manufacture of detergents, as precursors to more environmentally friendly refined oils, as monomers, and as precursors for many other types of products.
  • One method of making alpha olefins is via oligomerization of ethylene in a catalytic reaction involving various types of catalysts and/or catalyst systems.
  • Examples of catalysts and catalyst systems used commercially in the oligomerization of ethylene include alkylaluminum compounds, certain nickel-phosphine complexes, a titanium halide with a Lewis acid (e.g., diethylaluminum chloride), a selective 1-hexene catalyst system containing a chromium containing compound (e.g., a chromium carboxylate), a nitrogen containing ligand (e.g., a pyrrole) and a metal alkyl (e.g., alkylaluminum compounds), and a selective trimerization and/or tetramerization catalyst system using a metal complex of a compound having a diphosphinylaminyl group.
  • a Lewis acid e.g., diethylaluminum chloride
  • a selective 1-hexene catalyst system containing a chromium containing compound (e.g., a chromium carboxylate), a nitrogen containing ligand
  • oligomerization catalyst systems to produce alpha olefins are based upon metal complexes of pyridine bis-imines and metal complexes of a-diimine compounds having a metal complexing group, among others. These catalyst systems typically use an organoaluminum compound (e.g., aluminoxane) as a component of the catalyst system for olefin oligomerization.
  • organoaluminum compound e.g., aluminoxane
  • a process for forming an oligomer product comprising (a) introducing into a reaction zone (i) ethylene; (ii) a heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt where the first metal salt is an iron salt, a cobalt salt, or a combination thereof; (iii) a second metal salt wherein an equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex is at least 0.5: 1 and where the second metal salt is an iron salt, a cobalt salt, or any combination thereof; (iv) an organoaluminum compound; (v) optionally hydrogen; and (vi) optionally an organic reaction medium; and (b) forming an oligomer product in the reaction zone.
  • Also disclosed herein is a process for forming an oligomer product comprising (a) introducing into a reaction zone (i) ethylene; (ii) heteroatomic ligand; (iii) a metal salt where ( 1 ) the metal salt is an iron salt, a cobalt salt, or any combination thereof, and (2) an equivalent molar ratio of the metal salt to the heteroatomic ligand is at least 1.5: 1; (iv) an organoaluminum compound; (v) optionally hydrogen; and (vi) optionally an organic reaction medium; and (b) forming an oligomer product in the reaction zone.
  • Groups of elements of the periodic table are indicated using the numbering scheme found in the version of the periodic table of elements published in Chemical and Engineering News, 63(5), 27, 1985.
  • a group of elements can be indicated using a common name assigned to the group; for example alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Group 3-12 elements, and halogens for Group 17 elements, among others.
  • transitional term “comprising”, which is synonymous with “including,” “containing,” “having,” or “characterized by,” is inclusive or open-ended and does not exclude additional, unrecited elements or method steps.
  • a “consisting essentially of claim occupies a middle ground between closed claims that are written in a "consisting of format and fully open claims that are drafted in a "comprising" format.
  • a feedstock consisting essentially of a material A can include impurities typically present in a commercially produced or commercially available sample of the recited compound or composition.
  • a claim includes different features and/or feature classes (for example, a method step, feedstock features, and/or product features, among other possibilities), the transitional terms "comprising,” “consisting essentially of,” and “consisting of apply only to the feature class which is utilized and it is possible to have different transitional terms or phrases utilized with different features within a claim.
  • a method can comprise several recited steps (and other non-recited steps) but utilize a catalyst system preparation consisting of specific or alternatively, consist of specific steps and/or utilize a catalyst system comprising recited components and other non-recited components.
  • compositions and methods are described in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of or “consist of the various components or steps.
  • a trialkylaluminum compound is meant to encompass one trialkylaluminum compound, or mixtures or combinations of more than one trialkylaluminum compound unless otherwise specified.
  • first, second, and third can be utilized to differentiate multiple occurrences of a similar element.
  • a method can utilize two or more solvents in different steps of a method, or alternatively, two different solvents in a mixture.
  • the differentiating term can be applied to any element described herein when necessary to provide a differentiation. It should be understood that the numerical or alphabetical precedence of the differentiating terms do not imply a particular order or preference of the element in a method or compound described herein unless specified otherwise.
  • a general reference to a compound includes all structural isomers unless explicitly indicated otherwise; e.g., a general reference to a C 6 hydrocarbon refers to all hydrocarbon having 6 carbon atoms, a general reference to pentane includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, and a general reference to a butyl group includes an n-butyl group, a sec-butyl group, an iso-butyl group, and a tert-butyl group.
  • any general formula or name presented also encompasses all conformational isomers, regioisomers, and stereoisomers that can arise from a particular set of substituents.
  • a chemical "group” is described according to how that group is formally derived from a reference or "parent” compound, for example, by the number of hydrogen atoms formally removed from the parent compound to generate the group, even if that group is not literally synthesized in this manner.
  • These groups can be utilized as substituents or coordinated or bonded to metal atoms.
  • an "alkyl group” formally can be derived by removing one hydrogen atom from an alkane
  • an “alkylene group” formally can be derived by removing two hydrogen atoms from an alkane.
  • a more general term can be used to encompass a variety of groups that formally are derived by removing any number (“one or more") hydrogen atoms from a parent compound, which in this example can be described as an "alkane group,” and which encompasses an "alkyl group,” an “alkylene group,” and materials have three or more hydrogens atoms, as necessary for the situation, removed from the alkane.
  • alkane group an "alkane group”
  • materials have three or more hydrogens atoms, as necessary for the situation, removed from the alkane.
  • a substituent, ligand, or other chemical moiety can constitute a particular "group” implies that the well-known rules of chemical structure and bonding are followed when that group is employed as described.
  • substituted when used to describe a group, for example, when referring to a substituted analog of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in that group, and is intended to be non-limiting.
  • a group or groups can also be referred to herein as “unsubstituted” or by equivalent terms such as “non-substituted,” which refers to the original group in which a non-hydrogen moiety does not replace a hydrogen within that group.
  • “Substituted” is intended to be non-limiting and include inorganic substituents or organic substituents.
  • organic group is used herein in accordance with the definition specified by IUPAC: an organic substituent group, regardless of functional type, having one free valence at a carbon atom.
  • organiclene group refers to an organic group, regardless of functional type, derived by removing two hydrogen atoms from an organic compound, either two hydrogen atoms from one carbon atom or one hydrogen atom from each of two different carbon atoms.
  • organic group refers to a generalized group formed by removing one or more hydrogen atoms from carbon atoms of an organic compound.
  • an "organyl group,” an “organylene group,” and an “organic group” can contain organic functional group(s) and/or atom(s) other than carbon and hydrogen, that is, an organic group can comprise functional groups and/or atoms in addition to carbon and hydrogen.
  • organic functional group(s) and/or atom(s) other than carbon and hydrogen include halogens, oxygen, nitrogen, phosphorus, and the like.
  • functional groups include ethers, aldehydes, ketones, esters, sulfides, amines, phosphines, and so forth.
  • organyl group consisting essentially of inert functional groups refers to an organyl group (having a free valence on a carbon atom) wherein the organic functional group(s) and/or atom(s) other than carbon and hydrogen present in the functional group are restricted to those functional group(s) and/or atom(s) other than carbon and hydrogen which do not complex with a metal compound and/or are inert under the process conditions defined herein.
  • organyl group consisting essentially of inert functional groups further defines the particular organyl groups that can be present within the organyl group consisting essentially of inert functional groups.
  • organyl group consisting essentially of inert functional groups can refer to the presence of one or more inert functional groups within the organyl group.
  • organyl group consisting essentially of inert functional groups includes the hydrocarbyl group as a member (among other groups).
  • an "organylene group consisting essentially of inert functional groups” refers to an organic group formed by removing two hydrogen atoms from one or two carbon atoms of an organic compound consisting of inert functional groups and an "organic group consisting essentially of inert functional groups” refers to a generalized organic group consisting essentially of inert functional groups formed by removing one or more hydrogen atoms from one or more carbon atoms of an organic compound consisting of inert functional groups.
  • an "inert functional group” is a group which does not substantially interfere with the process described herein in which the material having an inert functional group takes part and/or does not complex with the metal compound of the metal complex.
  • the term “does not complex with the metal compound” can include groups that could complex with a metal compound but in particular molecules described herein may not complex with a metal compound due to its positional relationship within a ligand.
  • an ether group located at a para position of a substituted phenyl phosphinyl group in an N 2 - phosphinyl amidine can be an inert functional group because a single metal compound cannot complex with both the para ether group and the N 2 -phosphinyl amidine group of the same metal complex molecule.
  • the inertness of a particular functional group is not only related to the functional group's inherent inability to complex the metal compound but can also be related to the functional group's position within the metal complex.
  • Non-limiting examples of inert functional groups which do not substantially interfere with processes described herein can include halo (fluoro, chloro, bromo, and iodo), nitro, hydrocarboxy groups (e.g., alkoxy, and/or aroxy, among others), sulfidyl groups, and/or hydrocarbyl groups, among others.
  • hydrocarbon whenever used in this specification and claims refers to a compound containing only carbon and hydrogen. Other identifiers can be utilized to indicate the presence of particular groups in the hydrocarbon (e.g., halogenated hydrocarbon indicates that the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon).
  • hydrocarbyl group is used herein in accordance with the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from a hydrocarbon.
  • a “hydrocarbylene group” refers to a group formed by removing two hydrogen atoms from a hydrocarbon, either two hydrogen atoms from one carbon atom or one hydrogen atom from each of two different carbon atoms. Therefore, in accordance with the terminology used herein, a “hydrocarbon group” refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group) from a hydrocarbon.
  • a “hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” can be acyclic or cyclic groups, and/or can be linear or branched.
  • hydrocarbyl group can include rings, ring systems, aromatic rings, and aromatic ring systems, which contain only carbon and hydrogen.
  • Hydrocarbyl groups include, by way of example, aryl, arylene, arene, alkyl, alkylene, alkane, cycloalkyl, cycloalkylene, cycloalkane, aralkyl, aralkylene, and aralkane groups, among other groups, as members.
  • alkane whenever used in this specification and claims refers to a saturated hydrocarbon compound. Other identifiers can be utilized to indicate the presence of particular groups in the alkane (e.g., halogenated alkane indicates that the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the alkane).
  • alkyl group is used herein in accordance with the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from an alkane.
  • an “alkylene group” refers to a group formed by removing two hydrogen atoms from an alkane (either two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms).
  • alkane group is a general term that refers to a group formed by removing one or more hydrogen atoms (as necessary for the particular group) from an alkane.
  • An “alkyl group,” “alkylene group,” and “alkane group” can be acyclic or cyclic groups, and/or can be linear or branched unless otherwise specified.
  • Primary, secondary, and tertiary alkyl groups are derived by removal of a hydrogen atom from a primary, secondary, or tertiary carbon atom, respectively, of an alkane.
  • the n-alkyl group can be derived by removal of a hydrogen atom from a terminal carbon atom of a linear alkane.
  • a cycloalkane is a saturated cyclic hydrocarbon, with or without side chains, for example, cyclobutane.
  • Unsaturated cyclic hydrocarbons having one or more endocyclic double or one triple bond are called cycloalkenes and cycloalkynes, respectively.
  • Cycloalkenes and cycloalkynes having only one, only two, only three, etc... endocyclic double or triple bonds, respectively, can be identified by use of the term "mono,” "di,” "tri, etc.... within the name of the cycloalkene or cycloalkyne. Cycloalkenes and cycloalkynes can further identify the position of the endocyclic double or triple bonds.
  • a "cycloalkyl group” is a univalent group derived by removing a hydrogen atom from a ring carbon atom of a cycloalkane.
  • a 1 -methylcyclopropyl group and a 2-methylcyclopropyl group are illustrated as follows.
  • a "cycloalkylene group” refers to a group derived by removing two hydrogen atoms from a cycloalkane, at least one of which is a ring carbon.
  • a "cycloalkylene group” includes both a group derived from a cycloalkane in which two hydrogen atoms are formally removed from the same ring carbon, a group derived from a cycloalkane in which two hydrogen atoms are formally removed from two different ring carbons, and a group derived from a cycloalkane in which a first hydrogen atom is formally removed from a ring carbon and a second hydrogen atom is formally removed from a carbon atom that is not a ring carbon.
  • cycloalkane group refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group and at least one of which is a ring carbon) from a cycloalkane.
  • general cycloalkane groups include those having zero, one, or more than one hydrocarbyl substituent groups attached to a cycloalkane ring carbon atom (e.g., a methylcyclopropyl group) and is a member of the group of hydrocarbon groups.
  • the base name of the cycloalkane group having a defined number of cycloalkane ring carbon atoms refers to the unsubstituted cycloalkane group (including having no hydrocarbyl groups located on cycloalkane group ring carbon atom).
  • a substituted cycloalkane group having a specified number of ring carbon atoms refers to the respective group having one or more substituent groups (including halogens, hydrocarbyl groups, or hydrocarboxy groups, among other substituent groups) attached to a cycloalkane group ring carbon atom.
  • each substituent of the substituted cycloalkane group having a defined number of cycloalkane ring carbon atoms is limited to hydrocarbyl substituent group.
  • olefin whenever used in this specification and claims refers to hydrocarbon compounds that have at least one carbon-carbon double bond that is not part of an aromatic ring or an aromatic ring system.
  • olefin includes aliphatic and aromatic, cyclic and acyclic, and/or linear and branched hydrocarbons having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system unless specifically stated otherwise. Olefins having only one, only two, only three, etc. carbon-carbon double bonds can be identified by use of the term “mono,” "di,” “tri,” etc. within the name of the olefin. The olefins can be further identified by the position of the carbon-carbon double bond(s).
  • alkene whenever used in this specification and claims refers to a linear or branched aliphatic hydrocarbon olefin that has one or more carbon-carbon double bonds. Alkenes having only one, only two, only three, etc. such multiple bonds can be identified by use of the term “mono,” "di,” “tri,” etc. within the name. Alkenes can be further identified by the position of the carbon-carbon double bond(s). Other identifiers can be utilized to indicate the presence or absence of particular groups within an alkene. For example, a haloalkene refers to an alkene having one or more hydrogen atoms replaced with a halogen atom.
  • alpha olefin refers to an olefin that has a carbon-carbon double bond between the first and second carbon atoms of the longest contiguous chain of carbon atoms.
  • alpha olefin includes linear and branched alpha olefins unless expressly stated otherwise. In the case of branched alpha olefins, a branch can be at the 2- position (a vinylidene) and/or the 3 -position or higher with respect to the olefin double bond.
  • vinylene whenever used in this specification and claims refers to an alpha olefin having a branch at the 2-position with respect to the olefin double bond.
  • alpha olefin does not indicate the presence or absence of other carbon-carbon double bonds unless explicitly indicated.
  • linear alpha olefin refers to a non-branched alpha olefin having a carbon-carbon double bond between the first and second carbon atom.
  • normal alpha olefin whenever used in this specification and claims refers to a linear aliphatic mono-olefin having a carbon-carbon double bond between the first and second carbon atoms. It is noted that "normal alpha olefin” is not synonymous with “linear alpha olefin” as the term “linear alpha olefin” can include linear olefinic compounds having a double bond between the first and second carbon atoms and additional double bonds.
  • An aliphatic compound is an acyclic or cyclic, saturated or unsaturated, carbon compound, excluding aromatic compounds.
  • aliphatic group is a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group) from the carbon atom of an aliphatic compound. Aliphatic compounds and therefore aliphatic groups can contain organic functional group(s) and/or atom(s) other than carbon and hydrogen.
  • Aromatic compound is a compound containing a cyclically conjugated double bond system that follows the Hiickel (4n+2) rule and contains (4n+2) pi-electrons, where n is an integer from 1 to 5.
  • Aromatic compounds, arenes, and heteroarenes can be monocyclic (e.g., benzene, toluene, furan, pyridine, methylpyridine) or polycyclic unless otherwise specified.
  • Polycyclic aromatic compounds, arenes, and heteroarenes include, unless otherwise specified, compounds wherein the aromatic rings can be fused (e.g., naphthalene, benzofuran, and indole), compounds where the aromatic groups can be separate and joined by a bond (e.g., biphenyl or 4-phenylpyridine), or compounds where the aromatic groups are joined by a group containing linking atoms (e.g., carbon of the methylene group in diphenylmethane; oxygen of diphenyl ether; nitrogen of triphenyl amine; among others linking groups).
  • the term "substituted" can be used to describe an aromatic group, arene, or heteroarene wherein a non-hydrogen moiety formally replaces a hydrogen in the compound, and is intended to be non-limiting.
  • An "aromatic group” refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group and at least one of which is an aromatic ring carbon atom) from an aromatic compound.
  • the removed hydrogen atom must be from an aromatic ring carbon.
  • an "aromatic group” formed by removing more than one hydrogen atom from an aromatic compound at least one hydrogen atom must be from an aromatic hydrocarbon ring carbon.
  • an "aromatic group” can have hydrogen atoms removed from the same ring of an aromatic ring or ring system (e.g., phen-l,4-ylene, pyridin-2,3-ylene, naphth-l,2-ylene, and benzofuran-2,3-ylene), hydrogen atoms removed from two different rings of a ring system (e.g., naphth-l,8-ylene and benzofuran-2,7-ylene), or hydrogen atoms removed from two isolated aromatic rings or ring systems (e.g., bis(phen-4-ylene)methane).
  • an aromatic ring or ring system e.g., phen-l,4-ylene, pyridin-2,3-ylene, naphth-l,2-ylene, and benzofuran-2,3-ylene
  • hydrogen atoms removed from two different rings of a ring system e.g., naphth-l,8-ylene and benzofuran-2,7-y
  • An arene is aromatic hydrocarbon, with or without side chains (e.g., benzene, toluene, or xylene, among others).
  • An "aryl group” is a group derived from the formal removal of a hydrogen atom from an aromatic ring carbon of an arene. It should be noted that the arene can contain a single aromatic hydrocarbon ring (e.g., benzene, or toluene), contain fused aromatic rings (e.g., naphthalene or anthracene), and contain one or more isolated aromatic rings covalently linked via a bond (e.g., biphenyl) or non-aromatic hydrocarbon group(s) (e.g., diphenylmethane).
  • an "arylene group” refers to a group formed by removing two hydrogen atoms (at least one of which is from an aromatic ring carbon) from an arene.
  • An “arene group” refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group and at least one of which is an aromatic ring carbon) from an arene.
  • general arene groups include those having zero, one, or more than one hydrocarbyl substituent groups located on an aromatic hydrocarbon ring or ring system carbon atom (e.g., a toluene group or a xylene group, among others) and is a member of the group of hydrocarbon groups.
  • a phenyl group (or phenylene group) and/or a naphthyl group (or naphthylene group) refer to the specific unsubstituted arene groups (including no hydrocarbyl group located on an aromatic hydrocarbon ring or ring system carbon atom).
  • a substituted phenyl group or substituted naphthyl group refers to the respective arene group having one or more substituent groups (including halogens, hydrocarbyl groups, or hydrocarboxy groups, among others) located on an aromatic hydrocarbon ring or ring system carbon atom.
  • substituent groups including halogens, hydrocarbyl groups, or hydrocarboxy groups, among others
  • each substituent is limited to a hydrocarbyl substituent group.
  • an "aralkyl group” is an aryl-substituted alkyl group having a free valance at a non-aromatic carbon atom (e.g., a benzyl group, or a 2-phenyleth- 1 -yl group, among others).
  • an "aralkylene group” is an aryl-substituted alkylene group having two free valencies at a single non-aromatic carbon atom or a free valence at two non-aromatic carbon atoms
  • an "aralkane group” is a generalized aryl- substituted alkane group having one or more free valencies at a non-aromatic carbon atom(s).
  • general aralkane groups include those having zero, one, or more than one hydrocarbyl substituent groups located on an aralkane aromatic hydrocarbon ring or ring system carbon atom and is a member of the group of hydrocarbon groups.
  • specific aralkane groups specifying a particular aryl group e.g., the phenyl group in a benzyl group or a 2-phenylethyl group, among others refer to the specific unsubstituted aralkane groups (including no hydrocarbyl group located on the aralkane aromatic hydrocarbon ring or ring system carbon atom).
  • a substituted aralkane group specifying a particular aryl group refers to a respective aralkane group having one or more substituent groups (including halogens, hydrocarbyl groups, or hydrocarboxy groups, among others).
  • substituent groups including halogens, hydrocarbyl groups, or hydrocarboxy groups, among others.
  • each substituent is limited to a hydrocarbyl substituent group.
  • substituted aralkane groups specifying a particular aryl group which can be utilized as a member of the group of hydrocarbon groups (or a member of the general group of aralkane groups).
  • a "primary carbon atom group,” a “secondary carbon atom group,” a “tertiary carbon atom group,” and a “quaternary carbon atom group” describe the type of carbon atom which would be created when the group is attached to a base structure.
  • a “primary carbon atom group” is a group wherein the carbon atom bonded to the base structure is also bonded to three monovalent atoms (e.g., hydrogen or halides) in addition to the base structure.
  • a methyl group, a trifluormethyl group (among other group) attached to a base structure represent potential "primary carbon atom groups.”
  • a “secondary carbon atom group” is a group wherein the carbon atom bonded to the base structure is bonded to one other non- monovalent atom (e.g., carbon, nitrogen, or oxygen, among others) and two monovalent atoms.
  • An ethyl group, a 1-chloroeth-l -yl group, and a methoxymethyl group (among others) attached to a base structure represent potential "secondary carbon atom groups.”
  • a “tertiary carbon group” is a group wherein the carbon atom bonded to the base structure is bonded to two other non-monovalent atoms and one monovalent atom.
  • An isopropyl group, a 2-chloroprop-l -yl group, a phenyl group, and a 1 -methoxyethy- 1 -yl group (among others) attached to a base structure represent potential "tertiary carbon groups.”
  • a "quaternary carbon group” is a group wherein the carbon atom bonded to the base structure is also bonded to three other non-monovalent atoms.
  • a tert-butyl group and a 2-methoxyprop-2-yl group (among others) attached to a base structure represent potential "quaternary carbon groups.”
  • halide has its usual meaning; therefore, examples of halides include fluoride, chloride, bromide, and iodide.
  • room temperature or “ambient temperature” are used herein to describe any temperature from 15 °C to 35 °C wherein no external heat or cooling source is directly applied. Accordingly, the terms “room temperature” and “ambient temperature” encompass the individual temperatures and any and all ranges, subranges, and combinations of subranges of temperatures from 15 °C to 35 °C wherein no external heating or cooling source is directly applied.
  • atmospheric pressure is used herein to describe an earth air pressure wherein no external pressure modifying means is utilized. Generally, unless practiced at extreme earth altitudes, “atmospheric pressure” is about 1 atmosphere (alternatively, about 14.7 psi or about 101 kPa). References to gaseous, liquid, and/or solid materials refer to the physical state of the material at 25 °C and atmospheric pressure.
  • references to substitution patterns are taken to indicate that the indicated group(s) is (are) located at the indicated position and that all other non- indicated positions are hydrogen.
  • reference to a 4-substituted phenyl group indicates that there is a non-hydrogen substituent located at the 4- position and hydrogens located at the 2, 3, 5, and 6 positions.
  • reference to a 3-substituted naphth-2-yl indicates that there is a non-hydrogen substituent located at the 3- position and hydrogens located at the 1, 4, 5, 6, 7, and 8 positions.
  • references to compounds or groups having substitutions at positions in addition to the indicated position will be referenced using comprising or some other alternative language.
  • a reference to a phenyl group comprising a substituent at the 4- position refers to a group having a non- hydrogen atom at the 4- position and hydrogen or any other non-hydrogen group at the 2-, 3-, 5-, and 6- positions.
  • reaction zone effluent and it derivatives (e.g., oligomerization reaction zone effluent) generally refers to all the material which exits the reaction zone.
  • reaction zone effluent and its derivatives, can also be prefaced with other descriptors that limit the portion of the reaction zone effluent being referenced.
  • reaction zone effluent refers to all material exiting the reaction zone (e.g., product and solvent or diluent, among others), while the term “olefin reaction zone effluent” refers to only the olefins within the reaction zone effluent and the term “oligomer product reaction zone effluent” refers to oligomer product within the reaction zone effluent.
  • oligomerization refers to processes which produce a mixture of products containing at least 70 weight percent products containing from 2 to 30 ethylene units.
  • an "oligomer” is a product that contains from 2 to 30 ethylene units while an “oligomerization product” or “oligomer product” includes all products made by the process including the “oligomers” and products which are not “oligomers” (e.g., products which contain more than 30 ethylene units).
  • oligomer product and “oligomerization product” can be used interchangeably.
  • the Schulz-Flory K value can be determined using any two oligomers of the oligomer product which differs in the number of monomer units by 1.
  • Catalyst system productivity is defined as grams of a product produced per gram (or mole) of heteroatomic ligand metal salt complex or heteroatomic ligand in the catalyst system utilized in the oligomerization.
  • Catalyst system activity is defined as grams of a product produced per gram (or mole) of heteroatomic ligand metal salt complex or heteroatomic ligand utilized per unit of time (e.g., hour) of an oligomerization.
  • Catalyst system productivity and/or activity can be stated in terms of various products of an oligomerization and/or components of catalyst system.
  • the catalyst system productivity which can be utilized include (g oligomer product )/(g Fe), among other productivities.
  • the terms "contacted,” “combined,” and “in the presence of refer to any addition sequence, order, or concentration for contacting or combining the recited two or more components.
  • the combining or contacting of the components, according to the various methods described herein can occur in one or more contact zones under suitable contact conditions such as temperature, pressure, contact time, flow rates, etc. . . .
  • the contact zone can be disposed in a vessel (e.g., a storage tank, tote, container, mixing vessel, reactor, etc.), a length of pipe (e.g., a tee, inlet, injection port, or header for combining component feed lines into a common line), or any other suitable apparatus for bringing the components into contact, unless otherwise specified.
  • the processes can be carried out in a batch or continuous process as is suitable for a given aspect, unless otherwise specified.
  • a process can have multiple steps or can include features having a number of different elements (e.g., components in a catalyst system or components in an olefin oligomerization process, among other features). These steps and/or elements can be designated utilizing the series a), b), c), etc., i), ii), iii), etc., (a), (b), (c), etc., and/or (i), (ii), (iii), etc. (among other designation series) as necessary to provide a designation for each process step and/or element.
  • steps and/or elements can be designated utilizing the series a), b), c), etc., i), ii), iii), etc., (a), (b), (c), etc., and/or (i), (ii), (iii), etc. (among other designation series) as necessary to provide a designation for each process step and/or element.
  • simultaneously refers to a contact method wherein the two or more recited compounds, mixtures, streams, and/or compositions are contacted by flowing into a common junction, pot, vessel, or reactor, among others, at the same time.
  • substantially simultaneously refers to a contact method wherein, during the contact of two or more recited compounds, mixtures, streams, and/or compositions, the two or more recited compounds, mixtures, streams, and/or compositions are contacted such that for some period during the contact process the two or more recited compounds, mixtures, streams, and/or compositions flow into a common junction, pot, vessel, or reactor at the same time.
  • substantially simultaneously includes scenarios where the flow of one of the (or less than all of the) recited compounds, mixtures, streams, and/or compositions can be initiated into the common junction, pot, vessel, or reactor before the others and/or the flow of one of the (or less than all of the) recited compounds, mixtures, streams, and/or compositions into the common junction, pot, vessel, or reactor can be completed, stopped, or discontinued before the other recited compounds, mixtures, streams, and/or compositions.
  • the terms "simultaneously,” “simultaneously contact,” “contact simultaneously,” and their derivatives can be modified by the inclusion of a term providing a quantity of the each of the recited compounds, mixtures, streams, and/or compositions which can be contacted simultaneously indicate scenarios of various degrees of "substantially simultaneously,” “substantially simultaneously contact,” “contact substantially simultaneously,” and their derivatives.
  • At least 20 %, 30 %, 40 %, 50 %, 60 %, 70 %, 75 %, 80 %, 85 %, 90 %, 95 % of each of the recited compounds, mixtures, streams, and/or compositions can be "simultaneously contacted” or "contacted simultaneously.”
  • the percentages of the recited compounds, mixtures, streams, and/or compositions that can be "simultaneously contacted” or “contacted simultaneously” can be by weight (wt. %), by volume (volume %), or by mole (mole %).
  • recited compounds, mixtures, streams, and/or compositions that are “substantially simultaneously,” “substantially simultaneously contact,” “contact substantially simultaneously,” and their derivatives shall mean that at least 50 % of each of the recited compounds, mixtures, streams, and/or compositions can be "simultaneously contacted” or "contacted simultaneously.”
  • processes comprising a) introducing into a reaction zone (i) ethylene, (ii) a heteroatomic ligand first metal salt complex, (iii) a second metal salt, and (iv) an organoaluminum compound; and b) forming an oligomer product.
  • the heteroatomic ligand first metal salt complex comprises a heteroatomic ligand complexed to a first metal salt.
  • processes comprising a) introducing into a reaction zone (i) ethylene, (ii) a heteroatomic ligand, (iii) a metal salt, and (iv) an organoaluminum compound; and b) forming an oligomer product.
  • these processes can be processes for forming an oligomer product. Further disclosed herein is the use of a metal salt (or second metal salt depending on the particular process) for improving the productivity of any process (e.g., processes for forming an oligomer product) disclosed herein.
  • the processes further can comprise an optional introduction of hydrogen into the reaction zone.
  • the processes further can comprise an optional introduction of an organic reaction medium.
  • the organo groups of the organoaluminum compound can be substantially devoid of ⁇ , ⁇ -branched organo groups and/or ⁇ , ⁇ -branched organo groups.
  • the ethylene, the heteroatomic ligand first metal salt complex, the heteroatomic ligand, the first metal salt, the metal salt, and hydrogen can be contacted with or in one or more organic reaction medium(s).
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, conditions capable of forming an oligomer product.
  • the heteroatomic ligand and metal salt or the heteroatomic ligand first metal salt complex can be any heteroatomic ligand and metal salt or any heteroatomic ligand first metal salt complex that when contacted with ethylene as disclosed herein can form an oligomer product.
  • the processes described herein utilize a heteroatomic ligand first metal salt complex; or alternatively, a heteroatomic ligand and a metal salt.
  • the heteroatomic ligand or the heteroatomic ligand of the heteroatomic ligand first metal salt complex can comprise a bidentate metal salt complexing moiety or a tridentate metal salt complexing moiety; alternatively, a bidentate metal salt complexing moiety; or alternatively, a tridentate metal salt complexing moiety.
  • the heteroatomic ligand or the heteroatomic ligand of the heteroatomic ligand first metal salt complex can comprise at least one metal salt complexing moiety; alternatively, one or two metal salt complexing moieties; alternatively, one metal salt complexing moiety; or alternatively, two metal salt complexing moieties.
  • each metal salt complexing moiety of the heteroatomic ligand or the heteroatomic ligand of the heteroatomic ligand first metal salt complex can comprise at least two metal salt complexing groups selected from the group consisting of an imine group and an aromatic nitrogen atom containing group.
  • each metal salt complexing moiety of the heteroatomic ligand or the heteroatomic ligand of the heteroatomic ligand first metal salt complex can comprise at least two imine metal salt complexing group, at least two imine complexing groups and an aromatic nitrogen atom containing group, or an imine group and an aromatic nitrogen atom containing group; alternatively, at least two imine metal salt complexing group; alternatively, at least two imine complexing groups and an aromatic nitrogen atom containing group; or alternatively, an imine group and an aromatic nitrogen atom containing group.
  • the aromatic nitrogen atom containing group of any metal salt complexing moiety of the heteroatomic ligand or the heteroatomic ligand of the heteroatomic ligand first metal salt complex can be a pyrrole group, a pyridine group, a bipyridine (2,2'-bipyridine) group, or a phenanthroline group; alternatively, a pyridine group, a bipyridine (2,2' -bipyridine) group, or a phenanthroline group; alternatively, a pyridine group or a phenanthroline group; alternatively, a pyridine group; alternatively, a bipyridine (2,2 '-bipyridine) group; or alternatively, a phenanthroline group.
  • the pyrrole group, pyridine group, bipyridine (2,2'-bipyridine) group, or phenanthroline group can be unsubstituted or substituted; alternatively, unsubstituted; or alternatively, substituted.
  • Each substituent of a substituted pyrrole group, a substituted pyridine group, a substituted bipyridine (2,2'- bipyridine) group, or a substituted phenanthroline group independently can be a halide, an alkyl group, or a hydrocarboxy group; alternatively, a halide or an alkyl group; alternatively, a halide or a hydrocarboxy group; alternatively, an alkyl group or a hydrocarboxy group; alternatively, a halide; alternatively, an alkyl group; or alternatively, a hydrocarboxy group.
  • Halides, alkyl groups (general and specific), and hydrocarboxy groups (general and specific) that can be utilized as substituents are independently disclosed herein and can be utilized without limitation, and in any combination, to further describe a substituted pyrrole group, a substituted pyridine group, a substituted bipyridine (2,2 '-bipyridine) group, or a substituted phenanthroline group.
  • the heteroatomic ligand or the heteroatomic ligand of the heteroatomic ligand first metal salt complex can be an a-diimine, a pyridine bisimine, a phenanthroline imine, or any combination thereof; alternatively, an ⁇ -diimine or a pyridine bisimine; alternatively, an a-diimine; alternatively, a pyridine bisimine; or alternatively, a phenanthroline imine.
  • the heteroatomic ligand first metal salt complex can be an ⁇ -diimine first metal salt complex, a pyridine bisimine first metal salt complex, a phenanthroline imine first metal salt complex, or any combination thereof; alternatively, an ⁇ -diimine first metal salt complex; alternatively, a pyridine bisimine first metal salt complex; or alternatively, a phenanthroline imine first metal salt complex.
  • the a-diimine, the pyridine bisimine, the phenanthroline imine, the ⁇ -diimine first metal salt complex, the pyridine bisimine first metal salt complex, and the phenanthroline imine first metal salt complex are independent elements of any respective processes described herein in which they are utilized and are independently described herein. These independently described elements can be utilized in any combination, and without limitation, to further describe the processes which utilize these independent elements.
  • an ⁇ -diimine and a metal salt, or an ⁇ -diimine first metal salt complex can be utilized in the processes described herein.
  • the a-diimine, or the a- diimine of the a-diimine first metal salt complex disclosed herein can be any a-diimine, or any a- diimine of the a-diimine first metal salt complex disclosed herein, that when contacted with the other materials of the processes described herein (e.g., metal salt, ethylene, organoaluminum compound and/or any other appropriate reagent(s)), under the appropriate conditions, can form an oligomer product.
  • the ⁇ -diimine and the metal salt are independent elements of the processes described herein and are independently disclosed herein.
  • the independent descriptions of the ⁇ -diimine and the metal salt (or the ⁇ -diimine and the first metal salt of the ⁇ -diimine first metal salt complex) can be used without limitation, and in any combination, to further describe the processes that can be utilized in the aspects and/or embodiments of the processes described herein.
  • the ⁇ -diimine (or the a-diimine of the a-diimine first metal salt complex) can comprise only one ⁇ -diimine group; alternatively, at least two ⁇ -diimine groups; or alternatively, the ⁇ -diimine can comprise only two ⁇ -diimine groups.
  • the ⁇ -diimine or the a-diimine of the a-diimine first metal salt complex can be described as comprising i) an ⁇ -diimine group, ii) a first imine nitrogen group attached to a first imine nitrogen atom of the ⁇ -diimine group, and iii) a second imine nitrogen group attached to a second imine nitrogen atom of the ⁇ -diimine group.
  • the a-diimine group, first imine nitrogen group, and second imine nitrogen group are independent elements of the ⁇ -diimine or the a-diimine of the a-diimine first metal salt complex and each of these elements are independently described herein.
  • the independent elements of the ⁇ -diimine or the a-diimine of the a-diimine first metal salt complex can used without limitation, and in any combination, to further describe the ⁇ -diimine or the a-diimine of the a-diimine first metal salt complex.
  • the ⁇ -diimine (or the a-diimine of the a-diimine first metal salt complex) can be a bidentate ⁇ -diimine or a tridentate a-diimine; alternatively, a bidentate a-diimine; or alternatively, a tridentate a-diimine.
  • the tridentate ⁇ -diimine description does not necessarily imply that all of the ligating elements of the tridentate ⁇ -diimine complex to the metal salt.
  • the ⁇ -diimine group of the a-diimine (or the a-diimine of the a-diimine first metal salt complex) can be derived from an a-diacyl compound; or alternatively, an a-dione.
  • the ⁇ -diimine (or the a-diimine of the a-diimine first metal salt complex) can be described as comprising i) an ⁇ -diimine group derived from an a-diacyl compound, ii) a first imine nitrogen group attached to a first imine nitrogen atom of the ⁇ -diimine group, and iii) a second imine nitrogen group attached to a second imine nitrogen atom of the ⁇ -diimine group; or alternatively, the ⁇ -diimine (or the a- diimine of the a-diimine first metal salt complex) can be described as comprising i) an ⁇ -diimine group derived from an a-dione, ii) a first imine nitrogen group attached to a first imine nitrogen atom of the a- diimine group, and iii) a second imine nitrogen group attached to a second imine nitrogen atom of
  • the ⁇ -diacyl compound (or a-dione) can be an aliphatic ⁇ -diacyl compound (or aliphatic a-dione) or an aromatic ⁇ -diacyl compound (or aromatic a-dione); alternatively, an aliphatic ⁇ -diacyl compound (or aliphatic a-dione); or alternatively, an aromatic ⁇ -diacyl compound (or aromatic a-dione).
  • the ⁇ -diacyl compound (or a-dione), whether it is aliphatic or aromatic, can be a cyclic ⁇ -diacyl compound (or cyclic a-dione) or an acyclic ⁇ -diacyl compound (or acyclic a-dione); alternatively, a cyclic ⁇ -diacyl compound (or cyclic a-dione); or alternatively, an acyclic a-diacyl compound (or acyclic a-dione).
  • the ⁇ -diacyl compound (or ⁇ -dione), whether it is aliphatic or aromatic and/or cyclic or acyclic can be a C to C 6 o a-diacyl compound (or C to C 6 o a-dione), a C to C 45 a-diacyl compound (or C to C 5 a-dione), a C to C 30 a- diacyl compound (or C to C 30 a-dione), or C to C 20 a-diacyl compound (or C to C 20 a-dione).
  • R kl and R k2 independently can be an organyl group; alternatively, an organyl group consisting essentially of inert functional groups; or alternatively, a hydrocarbyl group.
  • the organyl groups which can be utilized as R kl and/or R k2 can be a Ci to C 30 , a Ci to C 20 , a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 organyl group.
  • the organyl groups consisting essentially of inert functional groups which can be utilized as R kl and/or R k2 independently can be a Ci to C 30 , a Ci to C 2 o, a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 organyl group consisting essentially of inert functional groups.
  • the hydrocarbyl groups which can be utilized as R kl and/or R k2 independently can be a Ci to C 0 , a Ci to C 20 , a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 hydrocarbyl group.
  • the a-dione from which the a-diimine group (or the a-diimine of the a-diimine first metal salt complex) can be derived can be an acyclic a-dione, a semicyclic a-dione, or a cyclic a- dione; alternatively, an acyclic a-dione; alternatively, a semicyclic a-dione; or alternatively, a cyclic a- dione.
  • R kl and R k2 are acyclic.
  • R kl and/or R k2 are or can comprise a cyclic structure wherein R kl and R k2 are not connected to form a ring or ring system containing both ketone carbon atoms of the a-dione group.
  • R kl and R k2 are connected to form a ring or ring system containing both ketone carbon atoms of the a-dione group.
  • the ring or ring system(s) can be saturated.
  • the ring or ring system(s) can contain carbon-carbon double (and/or triple) bonds.
  • the ring or ring system(s) can be a bicyclic ring system.
  • the ring or ring system(s) can comprise an aromatic ring or an aromatic ring system.
  • the a-dione can be 2,3-butanedione, a substituted 2,3-butanedione, 2,3-pentanedione, a substituted 2,3-pentanedione, 2,3-hexanedione, a substituted 2,3-hexanedione, 3,4- hexanedione, or a substituted 3,4-hexanedione.
  • the a-dione can be 2,3-butanedione, 2,3- pentanedione, 2,3-hexanedione, or 3,4-hexanedione.
  • the a-dione can be 2,3- butanedione; alternatively, 2,3-pentanedione; alternatively, 2,3-hexanedione; or alternatively, 3,4- hexanedione.
  • the a-dione can be benzil or a substituted benzil. In other aspects, the a-dione can be benzil.
  • the a-dione can be 1,2-cyclobutanedione, a substituted 1,2- cyclobutanedione, 1,2-cyclopentanedione, a substituted 1,2-cyclopentanedione, 1,2-cyclohexanedione, a substituted 1,2-cyclohexanedione, 1,2-cycloheptanedione, or a substituted 1,2-cycloheptanedione.
  • the a-dione can be 1,2-cyclopentanedione, a substituted 1,2- cyclopentanedione, 1,2-cyclohexanedione, or a substituted 1,2-cyclohexanedione.
  • the a-dione can be 1,2-cyclopentanedione, or 1,2-cyclohexanedione.
  • the a-dione can be 1,2-cyclopentanedione; or alternatively, 1,2-cyclohexanedione.
  • the a-dione can be bicyclo[2.2.1]hepta-l,2-dione, a substituted bicyclo[2.2.1]hepta-l,2-dione, bicyclo[2.2.2]octa-l,2-dione, a substituted bicyclo[2.2.2]octa- 1,2-dione, or camphorquinone.
  • the a-dione can be bicyclo[2.2.1]hepta-l,2-dione, bicyclo[2.2.2]octa-l,2-dione, or camphorquinone.
  • the a-dione can be camphorquinone.
  • the a-dione can be 1,2-benzoquinone, a substituted 1,2- benzoquinone, cyclohex-3-ene-l,2-dione, a substituted cyclohex-3-ene-l,2-dione, cyclopent-3-ene-l,2- dione, a substituted cyclopent-3-ene-l,2-dione, cyclohex-4-ene-l,2-dione, a substituted cyclohex-4-ene- 1,2-dione, 3,4-dihydro-l,2-naphthoquinone, a substituted 3,4-dihydro-l,2-naphtha- , quinone, 1,4- dihydronaphthoquinone, or a substituted 1,4-dihydronaphthoquinone.
  • the a-dione can be 1,2-benzoquinone, cyclohex-3-ene-l,2-dione, cyclopent-3-ene-l,2-dione, cyclohex-4-ene-l,2-dione, 3,4-dihydronaphthoquinone, or 1,4-dihydronaphthoquinone.
  • the a-dione can be 1,2-benzoquinone; alternatively, 3,4- dihydronaphthoquinone; or alternatively, 1,4-dihydronaphthanoquinone.
  • the a-dione can be a 1 ,2-naphthoquinone, a substituted 1 ,2-naphthoquinone, 2,3 -naphthoquinone, a substituted 2,3 -naphthoquinone, acenaphthenequinone, a substituted acenaphthenequinone, phenanthrenequinone, a substituted phenanthrenequinone, pyrenequinone, or a substituted pyrenequinone.
  • the a- dione can be 1 ,2-naphthoquinone, 2,3 -naphthoquinone, acenaphthenequinone, phenanthrenequinone, or pyrenequinone.
  • the a-dione can be acenaphthenequinone, phenanthrenequinone, or pyrenequinone.
  • the a-dione can be 1 ,2-naphthoquinone; alternatively, 2,3 -naphthoquinone; alternatively, acenaphthenequinone; alternatively, phenanthrenequinone; or alternatively, pyrenequinone.
  • each substituent independently can be a halide, an alkyl group, or a hydrocarboxy group; alternatively, a halide or an alkyl group; alternatively, a halide or a hydrocarboxy group; alternatively, an alkyl group or a hydrocarboxy group; alternatively, a halide; alternatively, an alkyl group; or alternatively, a hydrocarboxy group.
  • Halides, alkyl groups (general and specific), and hydrocarboxy groups (general and specific) that can be utilized as substituents are independently disclosed herein and can be utilized without limitation, and in any combination, to further describe the substituent of any substituted a-dione described herein.
  • the first imine group attached to the first imine nitrogen atom (first imine group for short) and/or second imine group attached to the second imine nitrogen atom (second imine group for short) of the a-diimine independently can be an organyl group; alternatively, an organyl group consisting essentially of inert functional groups; or alternatively, a hydrocarbyl group.
  • a bidentate a-diimine will have a first imine group and a second imine group which can be independently selected from an organyl group consisting essentially of inert functional groups (or a hydrocarbyl group).
  • the bidentate ⁇ -diimine can comprise i) an ⁇ -diimine group, ii) a first imine nitrogen group consisting of an organyl group consisting essentially of inert functional groups (or a hydrocarbyl group) attached to a first imine nitrogen atom of the ⁇ -diimine group and iii) a second imine nitrogen group consisting of an organyl group consisting essentially of inert functional groups (or a hydrocarbyl group) attached to a second imine nitrogen atom of the ⁇ -diimine group.
  • a tridentate ⁇ -diimine will have a first imine group selected from an organyl group consisting essentially of inert functional groups (or a hydrocarbyl group) while the second imine group is an organyl group.
  • the organyl group which is the second imine group can be described as a second imine group comprising (1) a metal salt complexing group (or a first metal salt complexing group for the ⁇ -diimine first metal salt complex) and (2) a linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to a second imine nitrogen atom of the ⁇ -diimine group.
  • the tridentate ⁇ -diimine can comprise i) an ⁇ -diimine group, ii) a first imine nitrogen group consisting of an organyl group consisting essentially of inert functional groups (or a hydrocarbyl group) attached to a first imine nitrogen atom of the ⁇ -diimine group, and iii) a second imine nitrogen group comprising (1) a metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) and (2) a linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to a second imine nitrogen atom of the ⁇ -diimine group.
  • the metal salt complexing group and the linking group (or the first metal salt complexing group and the linking group for the ⁇ -diimine first metal salt complex) of the second imine group comprising (1) a metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) and (2) a linking group linking the metal salt complexing group or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to a second imine nitrogen atom of the ⁇ -diimine group are independent elements of the second imine group and are independently described herein.
  • the independent description of the metal salt complexing group (or the first metal salt complexing group for the a-diimine first metal salt complex) and the linking group can be used without limitation and in any combination to further describe the second imine group comprising (1 ) a metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) and (2) a linking group linking the metal salt complexing group or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to a second imine nitrogen atom of the ⁇ -diimine group of an a-diimine.
  • the organyl groups which can be utilized as the first and/or second imine organyl groups independently can be a C ⁇ to C 20 , a C ⁇ to Cu, a C ⁇ to Cjo, or a Ci to C 5 organyl group.
  • the organyl groups consisting essentially of inert functional groups which can be utilized as the first and/or second imine organyl groups consisting essentially of inert functional groups independently can be a Ci to C 20 , a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 organyl group consisting essentially of inert functional groups.
  • the hydrocarbyl groups which can be utilized as the first and/or second imine hydrocarbyl groups independently can be a Ci to C 20 , a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 hydrocarbyl group.
  • the first imine group and the second imine group independently can be saturated or unsaturated, linear or branched, acyclic or cyclic, and/or aromatic or heteroaromatic.
  • the first imine group and/or second imine group can be a primary, a secondary, a tertiary, or a quaternary group; alternatively, a primary group; alternatively, a secondary group; alternatively, a tertiary group; or alternatively, a quaternary group.
  • imine nitrogen groups belong to the primary, secondary, tertiary, or quaternary imine nitrogen group classes.
  • the first imine group and/or second imine group independently can be an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl group, or a substituted aryl group.
  • the first imine group and/or second imine group independently can be an alkyl group or a substituted alkyl group; alternatively, a cycloalkyl group or a substituted cycloalkyl group; alternatively, an aryl group or a substituted aryl group; or alternatively, an alkyl group, a cycloalkyl group, or an aryl group.
  • the first imine group and/or second imine group independently can be an alkyl group; alternatively, a substituted alkyl group, alternatively, a cycloalkyl group; alternatively, a substituted cycloalkyl group; alternatively, an aryl group; or alternatively, a substituted aryl group.
  • the alkyl group which can be utilized as the first imine group and/or second imine group can be a Q to C 20 , a Ci to C 10 , or a Ci to C 5 alkyl group.
  • the substituted alkyl group which can be utilized as the first imine group and/or second imine group can be a Q to C 2 o, a Ci to C 10 , or a Ci to C 5 substituted alkyl group.
  • the cycloalkyl group which can be utilized as the first imine group and/or second imine group can be a C 4 to C 20 , a C 4 to Ci 5 , or a C 4 to Cm cycloalkyl group.
  • the substituted cycloalkyl group which can be utilized as the first imine group and/or second imine group can be a C 4 to C 2 o, a C 4 to Ci5, or a C 4 to Cm substituted cycloalkyl group.
  • the aryl group which can be utilized as the first imine group and/or second imine group can be a C 6 to C 2 o, a C 6 to Ci5, or a C 6 to Cm aryl group.
  • the substituted aryl group which can be utilized as the first imine group and/or second imine group can be a C 6 to C 2 o, a C 6 to C 15 , or a C 6 to C 10 substituted aryl group.
  • Each substituent of a substituted alkyl group (general or specific), a substituted cycloalkyl group (general or specific), a substituted aryl group (general or specific), and/or substituted aryl group (general or specific) can be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen; alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxy group.
  • Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups can be utilized without limitation to further describe the first imine group and/or second imine group.
  • the first imine nitrogen group and/or the second imine nitrogen group independently can be a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group.
  • the first imine nitrogen group and/or the second imine nitrogen group independently can be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group, a 3 -pentyl group, a 2- methyl-1 -butyl group, a tert-pentyl group, a 3 -methyl- 1 -butyl group, a 3-methyl-2-butyl group, or a neo- pentyl group.
  • the alkyl groups which can be utilized as the first imine nitrogen group and/or the second imine nitrogen group can be substituted.
  • Each substituent of a substituted alkyl group independently can be a halogen or a hydrocarboxy group; alternatively, a halogen; or alternatively, a hydrocarboxy group.
  • Substituent halogens and substituent hydrocarboxy groups are independently disclosed herein. These substituent halogens and substituent hydrocarboxy groups can be utilized without limitation to further describe a substituted alkyl group (general or specific) which can be utilized as the first imine nitrogen group and/or the second imine nitrogen group.
  • the first imine nitrogen group and/or the second imine nitrogen group can be a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, a substituted cyclohexyl group, an adamantyl group, or a substituted adamantyl group; alternatively, a cyclopentyl group or a substituted cyclopentyl group; alternatively, a cyclohexyl group or a substituted cyclohexyl group; alternatively, an adamantyl group or a substituted adamantyl group; alternatively, a cyclopentyl group; alternatively, a substituted cyclopentyl group; alternatively, a cyclohexyl group; alternatively, a substituted cyclohexyl group; alternatively, an adamantyl group; or alternatively, a substituted adamantyl group.
  • Each substituent of a substituted cycloalkyl group having a specified number of ring carbon atoms independently can be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxy group.
  • Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy (general and specific) groups are independently disclosed herein.
  • substituent halogens substituent hydrocarbyl groups, and substituent hydrocarboxy groups can be utilized without limitation to further describe a substituted cycloalkyl group (general or specific) which can be utilized as the first imine nitrogen group and/or the second imine nitrogen group.
  • the first imine nitrogen group and/or the second imine nitrogen group can be a phenyl group, a substituted phenyl group, a naphthyl group, or a substituted naphthyl group; alternatively, a phenyl group or a substituted phenyl group; alternatively, a naphthyl group, or a substituted naphthyl group; alternatively, a phenyl group; alternatively, a substituted phenyl group; alternatively, a naphthyl group; or alternatively, a substituted naphthyl group.
  • each substituted phenyl group which can be the first imine nitrogen group and/or the second imine nitrogen group can comprise a substituent at the 2- position, a substituent at the 3- position, a substituent at the 4- position, substituents at the 2- and 3- positions, substituents at the 2- and 4- positions, substituents at the 2- and 5- positions, substituents at the 3- and 5- positions, substituents at the 2- and 6- positions, or substituents at the 2-, 4-, and 6- positions; alternatively, a substituent at the 2- position, a substituent at the 4- position, substituents at the 2- and 4- positions, substituents at the 2- and 6- positions, or substituents at the 2-, 4-, and 6- positions; alternatively, substituents at the 2- and 6- positions or substituents at the 2-, 4-, and 6- positions; alternatively, a substituent at the 2- position; alternatively, a substituent at the 3- position; alternatively, a substituent at the 4- position; alternatively, substituents at the 2- and 3- positions; alternatively, substituent
  • the substituted phenyl group which can be utilized as the first imine nitrogen group and/or the second imine nitrogen group, can be a 2- substituted phenyl group, a 3 -substituted phenyl group, a 4-substituted phenyl group, a 2,3-disubstituted phenyl group, a 2,4-disubstituted phenyl group, a 2,5-disubstituted phenyl group, a 3,5-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group; alternatively, a 2- substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a 2,6- disubstituted phenyl group, or a 2,4,6-
  • one or more substituents of a multi-substituted phenyl group utilized as the first imine nitrogen group and/or the second imine nitrogen group can be the same or different; alternatively, all the substituents of a multi-substituted phenyl group can be the same; or alternatively, all the substituents of a multi-substituted phenyl group can be different.
  • Each substituent of a substituted phenyl group independently can be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxy group.
  • Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups are independently disclosed herein.
  • substituent halogens substituent hydrocarbyl groups, and substituent hydrocarboxy groups can be utilized without limitation to further describe a substituted phenyl group (general or specific) which can be utilized as the first imine nitrogen group and/or the second imine nitrogen group.
  • the substituted phenyl group which can be utilized as the first imine nitrogen group and/or the second imine nitrogen group can be a 2-alkylphenyl group, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,3-dialkylphenyl group, a 2,4-dialkylphenyl group, a 2,5-dialkylphenyl group, a 3,5-dialkylphenyl group, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6- dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively, a 2,6-dialkylphenyl group, or a 2,4,6- trialkylphenyl group; alternatively, a 2,6-dialkylpheny
  • alkyl substituents of a dialkylphenyl group (general or specific) or a trialkylphenyl group (general or specific) can be the same; or alternatively, the alkyl substituents of a dialkylphenyl group or trialkylphenyl group can be different.
  • Alkyl substituent groups are independently described herein and these alkyl substituent groups can be utilized, without limitation, to further describe any alkyl substituted phenyl group which can be utilized as the first imine nitrogen group and/or the second imine nitrogen group.
  • the substituted phenyl groups which can be the first imine nitrogen group and/or the second imine nitrogen group can be a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a 2,6-diisopropylphenyl group, or a 2,5-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, a 2,4,6-trimethylphenyl group, a 2,6- dimethyl-4-(tert-butyl)phenyl group, 2,6-dimethyl-4-(2,2-dimethylbenzyl)phenyl group, a 2,6-dimethyl-4- (l, l-diphenylethyl)phenyl group, or a 2,6-dimethyl-4-(l,l,3,3-tetramethylbutyl)phenyl group; alternatively, a 2,6-dimethylphenyl group, a 2,6-diethylpheny
  • the second imine nitrogen group can comprise (1) a metal salt complexing group (or the first metal salt complexing group for the a-diimine first metal salt complex) and (2) a linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to a second imine nitrogen atom of the ⁇ -diimine group.
  • the metal salt complexing group (or the first metal salt complexing group for the a-diimine first metal salt complex) and the linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to the second imine nitrogen atom of the ⁇ -diimine group are independent elements of the second imine group and are independently described herein.
  • the independent descriptions of the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) and the linking group can be used without limitation, and in any combination, to further describe the second imine group comprising ( 1 ) a metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) and (2) a linking group linking the metal salt complexing group (e.g. the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to a second imine nitrogen atom of the ⁇ -diimine group of an a- diimine.
  • the metal salt complexing group (or the first metal salt complexing group for the a- diimine first metal salt complex) can be any group comprising a heteroatom capable of complexing with the metal salt (or the first metal salt for the ⁇ -diimine first metal salt complex) and the linking group can be any group capable of linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to the second imine nitrogen atom of the ⁇ -diimine group.
  • the linking group includes all atoms between the second imine nitrogen atom and the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex).
  • the linking group includes all atoms between the second imine nitrogen atom and the heteroatom of the metal salt complexing (or the first metal salt complexing group for the a-diimine first metal salt complex) functional group.
  • the linking group is -CH 2 CH 2 - and the metal salt complexing group (or the first metal salt complexing group for the a- diimine first metal salt complex) is the ⁇ , ⁇ '-dimethylaminyl group, while in a 2-phenoxy ethyl group the linking group is -CH 2 CH 2 - and the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) is the phenoxy group.
  • the linking group includes all the atoms between the second imine nitrogen atom and the first atom within the ring containing the metal salt (or the first metal salt for the a-diimine first metal salt complex) complexing heteroatom of the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex).
  • the linking group is -CH 2 CH 2 - and the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) is the 2-pyridinyl group
  • the metal salt complexing group or the first metal salt complexing group for the ⁇ -diimine first metal salt complex
  • 1 -piperidinyl group the linking group is -CH 2 CH 2 - and the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) is the 1 -piperidinyl group.
  • the metal salt complexing group (or the first metal salt complexing group for the a-diimine first metal salt complex) can be any group comprising a heteroatom capable of complexing with the metal salt (or the first metal salt for the ⁇ -diimine first metal salt complex).
  • the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) can be a C 2 to C 30 group comprising a heteroatom, a C 2 to C 20 group comprising a heteroatom, a C 2 to Cio group comprising a heteroatom, or a C 2 to C 5 group comprising a heteroatom wherein the heteroatom is capable of complexing with the metal salt (or the first metal salt for the ⁇ -diimine first metal salt complex).
  • the metal salt complexing heteroatom (or the first metal salt complexing heteroatom for the ⁇ -diimine first metal salt complex) of the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) can be an oxygen, sulfur, nitrogen, or phosphorus; alternatively, oxygen or sulfur; or alternatively, nitrogen or phosphorus.
  • the metal salt complexing heteroatom (or the first metal salt complexing heteroatom for the a- diimine first metal salt complex) of the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) can be oxygen; alternatively, sulfur; alternatively, nitrogen; or alternatively, phosphorus.
  • the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) can contain additional heteroatoms which do not complex the metal salt (or the first metal salt for the ⁇ -diimine first metal salt complex) in the a- diimine metal salt complex (or the ⁇ -diimine first metal salt complex) such as inert heteroatoms (e.g. halides and silicon) and/or additional metal salt complexing heteroatom(s) (or the first metal salt complexing heteroatom(s) for the a-diimine first metal salt complex) which do not complex with the metal salt (or the first metal salt for the ⁇ -diimine first metal salt complex).
  • additional heteroatoms which do not complex the metal salt (or the first metal salt for the ⁇ -diimine first metal salt complex) in the a- diimine metal salt complex (or the ⁇ -diimine first metal salt complex)
  • additional heteroatoms which do not complex the metal salt (or the first metal salt for
  • the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) can be a dihydrocarbyl aminyl group, a di(substituted hydrocarbyl) aminyl group, a dihydrocarbyl phosphinyl group, a di(substituted hydrocarbyl) phosphinyl group, a hydrocarbyl etheryl group, a substituted hydrocarbyl etheryl group, a hydrocarbyl sulfidyl group, a substituted hydrocarbyl sulfidyl group, a furanyl group, a substituted furanyl group, a tetrahydrofuranyl group, a substituted tetrahydrofuranyl group, a pyridinyl group, a substituted pyridinyl group, a morphilinyl group, a substituted morphilin
  • the metal salt complexing group (or the first metal salt for the ⁇ -diimine first metal salt complex) can be a dihydrocarbyl aminyl group or a di(substituted hydrocarbyl) aminyl group; alternatively, a dihydrocarbyl phosphinyl group or a di(substituted hydrocarbyl) phosphinyl group; alternatively, a hydrocarbyl etheryl group or a substituted hydrocarbyl etheryl group; or alternatively, a hydrocarbyl sulfidyl group or a hydrocarbyl sulfidyl group.
  • the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) can be a dihydrocarbyl aminyl group; alternatively, a di(substituted hydrocarbyl) aminyl group; alternatively, a dihydrocarbyl phosphinyl group; or alternatively, a di(substituted hydrocarbyl) phosphinyl group.
  • Each substituent of a substituted metal salt complexing group independently can be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen; alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxy group.
  • Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups are independently disclosed herein.
  • substituent halogens substituent hydrocarbyl groups, and substituent hydrocarboxy groups can be utilized without limitation to further describe a substituted metal salt complexing group (or a substituted first metal salt complexing group for the ⁇ -diimine first metal salt complex).
  • Each hydrocarbyl group of any metal salt complexing group (or any first metal salt complexing group for the ⁇ -diimine first metal salt complex) having a hydrocarbyl group disclosed herein independently can be a Q to C 2 o, a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 hydrocarbyl group while each substituted hydrocarbyl group of a metal salt complexing group (or a first metal salt complexing group for the ⁇ -diimine first metal salt complex) having a substituted hydrocarbyl group disclosed herein independently can be a Ci to C 2 o, a Ci to Ci 5 , a Ci to Cm, or a Ci to C 5 substituted hydrocarbyl group.
  • each hydrocarbyl/substituted hydrocarbyl group of a metal salt complexing group (or the first metal salt complexing group for the a-diimine first metal salt complex) having a hydrocarbyl/substituted hydrocarbyl group described herein independently can be an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl group, or a substituted aryl group; alternatively, an alkyl group or a substituted alkyl group; alternatively, a cycloalkyl group or a substituted cycloalkyl group; alternatively, an aryl group or a substituted aryl group; alternatively, an alkyl group, a cycloalkyl group, or an aryl group; alternatively, an alkyl group; alternatively, a substituted alkyl group, alternatively, a cycloalkyl group; alternatively, a substituted a
  • Each substituent of a substituted alkyl group (general or specific), a substituted cycloalkyl group (general or specific), a substituted aryl group (general or specific), and/or a substituted aralkyl group (general or specific) can be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen; alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxy group.
  • Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups can be utilized without limitation to further describe a substituted metal salt complexing group (or the substituted first metal salt complexing group for the a-diimine first metal salt complex).
  • the alkyl group of any metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) having an alkyl group disclosed herein independently can be a Ci to C 2 o, a Ci to Cm, or a Ci to C 5 alkyl group while the substituted alkyl group of any metal salt complexing group (or any first metal salt complexing group for the ⁇ -diimine first metal salt complex) having a substituted alkyl group disclosed herein independently can be a Ci to C 2 o, a Ci to C 10 , or a Ci to C 5 substituted alkyl group.
  • the alkyl group of any metal salt complexing group (or the first metal salt complexing group for the a- diimine first metal salt complex) having an alkyl group disclosed herein independently can be a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group.
  • the alkyl group of any metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) having an alkyl group disclosed herein independently can be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group, a 3 -pentyl group, a 2-methyl- 1 -butyl group, a tert- pentyl group, a 3 -methyl- 1 -butyl group, a 3-methyl-2-butyl group, or a neo-pentyl group.
  • the alkyl groups which can be utilized as the alkyl group of any metal salt complexing group (or any first metal salt complexing group for the a-diimine first metal salt complex) having an alkyl group disclosed herein can be substituted.
  • Each substituent of a substituted alkyl group independently can be a halogen or a hydrocarboxy group; alternatively, a halogen; or alternatively, a hydrocarboxy group.
  • Substituent halogens and substituent hydrocarboxy groups are independently disclosed herein.
  • substituent halogens and substituent hydrocarboxy groups can be utilized without limitation to further describe a substituted alkyl group which can be utilized as the substituted alkyl group of a metal salt complexing group (or a first metal salt complexing group for the a- diimine first metal salt complex).
  • the cycloalkyl group of any metal salt complexing group (or any first metal salt complexing group for the a-diimine first metal salt complex) having a cycloalkyl group disclosed herein independently can be a C 4 to C 2 o, a C 4 to C 15 , or a C 4 to C 10 cycloalkyl group while the substituted cycloalkyl group of any metal salt complexing group (or any first metal salt complexing group for the ⁇ -diimine first metal salt complex) having a substituted cycloalkyl group disclosed herein independently can be a C 4 to C 2 o, a C 4 to C 15 , or a C 4 to C 10 substituted cycloalkyl group.
  • each cycloalkyl/substituted cycloalkyl group of a metal salt complexing group (or a first metal salt complexing group for the ⁇ -diimine first metal salt complex) having a cycloalkyl/substituted cycloalkyl group described herein independently can be cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, or a substituted cyclohexyl group; alternatively, a cyclopentyl group or a substituted cyclopentyl group; alternatively, a cyclohexyl group or a substituted cyclohexyl group; alternatively, a cyclopentyl group; alternatively, a substituted cyclopentyl group; alternatively, a cyclohexyl group; or alternatively, a substituted cyclohexyl group.
  • Each substituent of a substituted cycloalkyl group having a specified number of ring carbon atoms independently can be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxy group.
  • Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy (general and specific) groups are independently disclosed herein.
  • substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups can be utilized without limitation to further describe a substituted cycloalkyl group which can be utilized as the substituted cycloalkyl group of a metal salt complexing group (or a first metal salt complexing group for the ⁇ -diimine first metal salt complex).
  • the aryl group of any metal salt complexing group (or any first metal salt complexing group for the ⁇ -diimine first metal salt complex) having an aryl group disclosed herein independently can be a C 6 to C 2 o, a C 6 to Ci 5 , or a C 6 to Ci 0 aryl group while the substituted aryl group of any metal salt complexing group (or any first metal salt complexing group for the a-diimine first metal salt complex) having a substituted aryl group disclosed herein independently a C 6 to C 2 o, a C 6 to Ci5, or a C 6 to Cm substituted aryl group.
  • the aryl/substituted aryl group of any metal salt complexing group (or any first metal salt complexing group for the a-diimine first metal salt complex) having an aryl/substituted aryl group disclosed herein independently can be a phenyl group or a substituted phenyl group; alternatively, a phenyl group; or alternatively, a substituted phenyl group.
  • the substituted phenyl group of any metal salt complexing group (or any first metal salt complexing group for the ⁇ -diimine first metal salt complex) having a substituted phenyl group independently can be a C 6 to C 2 o, a C 6 to C 15 , or a C 6 to C 10 substituted phenyl group.
  • the substituted phenyl group of any metal salt complexing group (or any first metal salt complexing group for the ⁇ -diimine first metal salt complex) having a substituted phenyl group independently can be a 2-substituted phenyl group, a 3 -substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenyl group; alternatively, a 3 -substituted pheny
  • one or more substituents of a multi-substituted phenyl group utilized as a substituted phenyl group for any metal salt complexing group (or any first metal salt complexing group for the ⁇ -diimine first metal salt complex) having a substituted aryl group or substituted phenyl group described herein can be the same or different; alternatively, all the substituents of a multi-substituted cycloalkyl group can be the same; or alternatively, all the substituents of a multi- substituted cycloalkyl group can be different.
  • Each substituent of a substituted aryl group (general or specific) or substituted phenyl group (general or specific) which can be utilized as a substituted aryl group or a substituted phenyl group for any metal salt complexing group (or any first metal salt complexing group for the ⁇ -diimine first metal salt complex) having a substituted aryl group or substituted phenyl group independently can be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxy group.
  • Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups can be utilized without limitation to further describe a substituted aryl group (general or specific) or a substituted phenyl group (general or specific) which can be utilized as utilized as a substituted aryl group or a substituted phenyl group for any metal salt complexing group (or any first metal salt complexing group for the a-diimine first metal salt complex) having a substituted aryl group or substituted phenyl group.
  • the substituted phenyl group of any metal salt complexing group (or any first metal salt complexing group for the a-diimine first metal salt complex) having a substituted phenyl group disclosed herein independently can be a 2-alkylphenyl group, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group or a 4-alkylphenyl group; alternatively, a 2,4-dialkylphenyl group;
  • one or more alkyl group substituents of a multi-alkyl group substituted phenyl group utilized as a substituted phenyl group for any metal salt complexing group (or any first metal salt complexing group for the ⁇ -diimine first metal salt complex) having an alkyl substituted phenyl group described herein can be the same or different; alternatively, all the substituents of a multi-alkyl group substituted cycloalkyl group can be the same; or alternatively, all the substituents of a multi-alkyl group substituted cycloalkyl group can be different.
  • Alkyl substituent groups are independently described herein and these alkyl substituent groups can be utilized, without limitation, to further describe any alkyl substituted phenyl group which can be utilized as a substituted phenyl group for any metal salt complexing group (or any first metal salt complexing group for the ⁇ -diimine first metal salt complex) having a substituted aryl group or substituted phenyl group described herein.
  • the alkyl substituents of a dialkylphenyl group (general or specific) or a trialkylphenyl group (general or specific) can be the same; or alternatively, the alkyl substituents of a dialkylphenyl group (general or specific) or a trialkyl phenyl group (general or specific) can be different.
  • the substituted phenyl group of any metal salt complexing group (or any first metal salt complexing group for the ⁇ -diimine first metal salt complex) having a substituted phenyl group disclosed herein independently can be a 3,5-dimethylphenyl group.
  • the linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to the second imine nitrogen atom of the a-diimine group can be a bond or an organyl group; alternatively, a bond or an organyl group consisting essentially of inert functional groups; alternatively, a bond or a hydrocarbyl group; alternatively, an organyl group; alternatively, an organyl group consisting essentially of inert functional groups; alternatively, a hydrocarbyl group; or alternatively, a bond.
  • the organyl linking group linking the metal salt complexing group (or the first metal salt complexing group for the a-diimine first metal salt complex) to the second imine nitrogen atom of the a-diimine group can be a Ci to C 20 , a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 organyl group.
  • the organyl group consisting essentially of inert functional groups linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to the second imine nitrogen atom of the ⁇ -diimine group can be a Ci to C 20 , a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 organyl group consisting essentially of inert functional groups.
  • the hydrocarbyl group linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to the second imine nitrogen atom of the ⁇ -diimine group can be a Q to C 20 , a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 hydrocarbyl group.
  • the hydrocarbyl group linking group linking the metal salt complexing group (or the first metal salt complexing group for the a-diimine first metal salt complex) to the second imine nitrogen atom of the ⁇ -diimine group can be a Ci to C 20 , a Ci to Ci5, a Ci to Cio, or a Ci to C 5 alkyl group.
  • the linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to the second imine nitrogen atom of the ⁇ -diimine group can be saturated or unsaturated, linear or branched, acyclic or cyclic, and/or aliphatic or aromatic.
  • the linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to the second imine nitrogen atom of the a- diimine group can be -(C(R L1 ) 2 ) m -, a phenyl- 1,2-ene group, or a substituted phenyl- 1,2-ene group; alternatively, a phenyl- 1,2-ene group or a substituted phenyl- 1,2-ene group; alternatively, -(C(R L1 ) 2 ) m -; alternatively, a phenyl- 1,2-ene group; alternatively, a substituted phenyl- 1,2-ene group.
  • R L1 and m are independent elements of the linking group having the structure -(C(R L1 ) 2 ) m - and are independently described herein.
  • the independent descriptions of R L1 and m can be utilized without limitation, and in any combination, to further describe the linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to the second imine nitrogen atom of the ⁇ -diimine group having the structure -(C(R L1 ) 2 ) m -.
  • each R L1 independently can be hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group; alternatively, hydrogen, a methyl group, or a propyl group.
  • m can be an integer from 1 to 5; alternatively, 2 or 3; alternatively, 2; or alternatively, 3.
  • Each substituent of a substituted phenyl- 1 ,2-ene group which can be utilized as the linking group linking the metal salt complexing group (or the first metal salt complexing group for the a-diimine first metal salt complex) to the second imine nitrogen atom of the a-diimine group can be a halide, an alkyl group, or an alkoxy group; alternatively, a halide or an alkyl group; alternatively, a halide and an alkoxy group; alternatively, an alkyl group or an alkoxy group; alternatively, a halide; alternatively, an alkyl group; or alternatively, an alkoxy group.
  • Halides, alkyl groups (general and specific), and alkoxy groups (general and specific) that can be utilized as substituents are independently disclosed herein and can be utilized without limitation, and in any combination, to further describe the substituted phenyl- 1,2-ene group which can be utilized as the linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to the second imine nitrogen atom of the a- diimine group.
  • the linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to the second imine nitrogen atom of the ⁇ -diimine group can be a methylene group, an eth-l ,2-ylene group, a prop-l ,3-ylene group, a dimethylmethylene group, a butyl- l ,4-ene group or a phen-l ,2-ylene group.
  • the linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to the second imine nitrogen atom of the a-diimine group can be an eth-l ,2-ylene group, a prop- l ,3-ylene group, or a phen-l ,2-ylene group; alternatively, an eth-l ,2-ylene group, or a prop-l ,3-ylene group; alternatively, an eth-l ,2-ylene group; alternatively, a prop- l ,3 -ylene group; or alternatively, a phen- l ,2-ylene group.
  • the second imine group comprising (1 ) a metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) and (2) a linking group linking the metal salt complexing group (or the first metal salt complexing group for the a-diimine first metal salt complex) to a second imine nitrogen atom of the ⁇ -diimine group
  • the second imine group comprising (1 ) a metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) and (2) a linking group linking the metal salt complexing group (or the first metal salt complexing group for the ⁇ -diimine first metal salt complex) to a second imine nitrogen atom of the a- diimine group
  • the second imine group comprising (1) a metal salt complexing group (e.g. the first metal salt complexing group for the a-diimine first metal salt complex) and (2) a linking group linking the metal salt complexing group (e.g.
  • the first metal salt complexing group for the a-diimine first metal salt complex) to a second imine nitrogen atom of the ⁇ -diimine group can be a 2-(diisopropylphosphinyl)ethyl group, a 2-(diphenylphosphinyl)ethyl group, a 2-(di-(3,5-dimethylphenyl)phosphinyl)ethyl group; alternatively, a 3-(diisopropyl- phosphinyl)propyl group, a 3 -(diphenylphosphinyl)propyl group, a 3-(di-(3,5-dimethylphenyl)- phosphinyl)propyl group; alternatively, a 2-(diisopropylphosphinyl)ethyl group; alternatively, a 2- (diphenylphosphinyl)ethyl group; or alternatively, a 2-(di-
  • a pyridine bisimine and a metal salt, or a pyridine bisimine first metal salt complex can be utilized in the processes described herein.
  • the pyridine bisimine or the pyridine bisimine of the pyridine bisimine first metal salt complex disclosed herein can be any pyridine bisimine, or any pyridine bisimine of the pyridine bisimine first metal salt complex disclosed herein, that when contacted with the other materials of the process described herein (e.g., metal salt, ethylene, organoaluminum compound and/or any other appropriate reagent(s)), under the appropriate conditions, can form an oligomer product.
  • the pyridine bisimine and the metal salt, or pyridine bisimine first metal salt complexes are independent elements of the processes described herein and are independently disclosed herein.
  • the independent descriptions of the pyridine bisimine and the metal salt, or pyridine bisimine first metal salt complexes (or the pyridine bisimine and the first metal salt of the pyridine bisimine first metal salt complex) can be used without limitation, and in any combination, to further describe the processes that can be utilized in the aspects and/or embodiments of the processes described herein.
  • the pyridine bisimine (or the pyridine bisimine of the pyridine bisimine first metal salt complex) can comprise only one pyridine bisimine group; alternatively, at least two pyridine bisimine groups; or alternatively, the pyridine bisimine can comprise only two pyridine bisimine groups.
  • the pyridine bisimine or the pyridine bisimine of the pyridine bisimine first metal salt complex can have Structure PBI I or Structure PBI II; alternatively, Structure PBI I; or alternatively, Structure PBI II.
  • any pyridine bisimine first metal salt complex can have Structure PBIMC I or Structure PBIMC II; alternatively, Structure PBIMC I; or alternatively, Structure PBIMC II.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 of the pyridine bisimine having Structure PBI I or the pyridine bisimine first metal salt complex having Structure PBIMC I are independent elements of the pyridine bisimine having Structure PBI I and the pyridine bisimine first metal salt complex having Structure PBIMC I and are independently described herein.
  • the independent descriptions of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 can utilized without limitation, and in any combination, to further describe the pyridine bisimine having Structure PBI I and/or the pyridine bisimine first metal salt complex having Structure PBIMC I.
  • R 2 , R 6 , R 7 , L 1 , and L 2 of the pyridine bisimine having Structure PBI II or the pyridine bisimine first metal salt complex having Structure PBIMC II are independent elements of the pyridine bisimine having Structure PBI II and the pyridine bisimine first metal salt complex having Structure PBIMC II and are independently described herein.
  • the independent descriptions of R 2 , R 6 , R 7 , L 1 , and L 2 can utilized without limitation, and in any combination, to further describe the pyridine bisimine having Structure PBI II and/or the pyridine bisimine first metal salt complex having Structure PBIMC II.
  • first metal salt MX n
  • MX n is independently described herein and can be combined, without limitation, with the independently described R , R , R , R , R , R , L , and L to further describe the appropriate pyridine bisimine first metal salt complex structure described herein which have an R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , L 1 , and/or L 2 .
  • R 1 , R 2 , and/or R 3 of the respective pyridine bisimines and pyridine bisimine first metal salt complexes which have an R 1 , R 2 , and/or R 3 , independently can be hydrogen, an inert functional group, or an organyl group; alternatively, hydrogen or an organyl group; alternatively, an inert functional group or an organyl group; alternatively, hydrogen, an inert functional group, or an organyl group consisting essentially of inert functional groups; alternatively, hydrogen or an organyl group consisting essentially of inert functional groups; alternatively, an inert functional group or an organyl group consisting essentially of inert functional groups; alternatively, hydrogen, an inert functional group, or a hydrocarbyl group; alternatively, hydrogen or a hydrocarbyl group; alternatively, an inert functional group or a hydrocarbyl group; alternatively, hydrogen or an inert functional group or a hydrocarbyl group; alternatively, hydrogen or an in
  • the R 1 , R 2 , and/or R 3 organyl groups of the pyridine bisimines and/or pyridine bisimine first metal salt complexes which have an R 1 , R 2 , and/or R 3 group independently can be a Ci to C 20 , a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 organyl group.
  • the R 1 , R 2 , and/or R 3 organyl groups consisting essentially of inert functional groups, of the pyridine bisimines and/or pyridine bisimine first metal salt complexes which have an R 1 , R 2 , and/or R 3 group, independently can be a Q to C 20 , a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 organyl group consisting essentially of inert functional groups.
  • the R 1 , R 2 , and/or R 3 hydrocarbyl groups of the pyridine bisimines and/or pyridine bisimine first metal salt complexes which have an R 1 , R 2 , and/or R 3 group independently can be a Ci to C 20 , a Ci to Ci 5 , a Ci to Cio, or a Ci to C 5 hydrocarbyl group.
  • the hydrocarbyl group which can be utilized as R 1 , R 2 , and/or R 3 of the pyridine bisimines and pyridine bisimine first metal salt complexes which have an R 1 , R 2 , and/or R 3 hydrocarbyl group independently can be a Ci to C 20 , a Ci to Ci 0 , or a Ci to C 5 alkyl group.
  • the R 1 , R 2 , and/or R 3 alkyl groups of the pyridine bisimines and pyridine bisimine first metal salt complexes which have an R 1 , R 2 , and/or R 3 alkyl group independently can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group.
  • the R 1 , R 2 , and/or R 3 alkyl groups of the pyridine bisimines and pyridine bisimine first metal salt complexes which have an R 1 , R 2 , and/or R 3 alkyl group independently can be a methyl group, an ethyl group, an iso-propyl (2-propyl) group, a tert-butyl (2-methyl-2 -propyl) group, or a neopentyl (2,2-dimethyl-l -propyl) group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, a n-propyl (1 -propyl) group; alternatively, an iso-propyl (2-propyl) group; alternatively, a tert-butyl (2-methyl-2 -propyl) group; or alternatively, a neopentyl (2,2-dimethyl- 1 -propyl) group.
  • R 1 , R 2 , and/or R 3 of the pyridine bisimines which have an R 1 , R 2 , and/or R 3 group each can be hydrogen.
  • the pyridine bisimine can have Structure PBI III or Structure PBI IV; alternatively, Structure PBI III; or alternatively, Structure PBI IV.
  • R 1 , R 2 , and R 3 of the pyridine bisimine first metal salt complexes which have an R 1 , R 2 , and/or R 3 group each can be hydrogen.
  • the pyridine bisimine first metal salt complexes can have Structure PBIMC III or Structure PBIMC IV; alternatively, Structure PBIMC III; or alternatively, Structure PBIMC IV.
  • R 4 , R 5 , R 6 , and R 7 of the pyridine bisimine having Structure PBI III or the pyridine bisimine first metal salt complex having Structure PBIMC III are independent elements of the pyridine bisimine having Structure PBI III and the pyridine bisimine first metal salt complex having Structure PBIMC III and are independently described herein.
  • the independent descriptions of R 4 , R 5 , R 6 , and R 7 can be utilized without limitation, and in any combination, to further describe the pyridine bisimine having Structure PBI
  • R 6 , R 7 , L 1 , and L 2 of the pyridine bisimine having Structure PBI IV or the pyridine bisimine first metal salt complex having Structure PBIMC IV are independent elements of the pyridine bisimine having Structure PBI IV and the pyridine bisimine first metal salt complex having Structure PBIMC IV and are independently described herein.
  • the independent descriptions of R 6 , R 7 , L 1 , and L 2 can be utilized without limitation, and in any combination, to further describe the pyridine bisimine having Structure PBI
  • the first metal salt, MX n is independently described herein and can be combined, without limitation, with the independently described R 4 , R 5 , R 6 , R 7 , L 1 , and L 2 to further describe the appropriate pyridine bisimine first metal salt complex structure described herein which have an R 4 , R 5 , R 6 , R 7 , L 1 , and/or L 2 .
  • R 4 and/or R 5 of the pyridine bisimines and pyridine bisimine first metal salt complexes which have an R 4 and/or R 5 , independently can be hydrogen or an organyl group; alternatively, hydrogen or an organyl group consisting essentially of inert functional groups; alternatively, hydrogen or a hydrocarbyl group; alternatively, hydrogen; alternatively, an organyl group; alternatively, an organyl group consisting essentially of inert functional groups; or alternatively, a hydrocarbyl group.
  • the R 4 and/or R 5 organyl groups of the pyridine bisimines and pyridine bisimine first metal salt complexes which have an R 4 and/or R 5 group independently can be a Ci to C 20 , a Ci to Ci 5 , a Ci to Cio, or a Ci to C 5 organyl group.
  • the R 4 and/or R 5 organyl groups consisting essentially of inert functional groups, of the pyridine bisimines and pyridine bisimine first metal salt complexes which have an R 4 and/or R 5 group independently can be a Ci to C 20 , a Ci to Ci 5 , a Ci to Ci 0 , or a Ci to C 5 organyl group consisting essentially of inert functional groups.
  • the R 4 and/or R 5 hydrocarbyl groups of the pyridine bisimines and pyridine bisimine first metal salt complexes which have an R 4 and/or R 5 group independently can be a Ci to C 20 , a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 hydrocarbyl group.
  • the R 4 and/or R 5 hydrocarbyl groups of the pyridine bisimines and pyridine bisimine first metal salt complexes which have an R 4 and/or R 5 group independently can be a Ci to C 2 o, a Ci to C 10 , or a Ci to C 5 alkyl group.
  • the R 4 and/or R 5 alkyl groups of the pyridine bisimines and pyridine bisimine first metal salt complexes which have an R 4 and/or R 5 group independently can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group.
  • the R 4 and/or R 5 alkyl groups of the pyridine bisimines and pyridine bisimine first metal salt complexes which have an R 4 and/or R 5 group independently can be a methyl group, an ethyl group, an iso-propyl (2-propyl) group, a tert-butyl (2-methyl -2 -propyl) group, or a neopentyl (2,2-dimethyl-l -propyl) group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, a n-propyl (1 -propyl) group; alternatively, an iso-propyl (2-propyl) group; alternatively, a tert-butyl (2-methyl-2-propyl) group; or alternatively, a neopentyl (2,2-dimethyl-l -propyl) group.
  • R 1 and R 4 and/or R 3 and R 5 can be joined to form a ring or a ring system containing two carbon atoms of the pyridine group and the carbon atom of the imine group.
  • L 1 represents the joined R 3 and R 5 while L 2 represents the joined R 1 and R 4 .
  • L 1 and/or L 2 of a pyridine bisimine or pyridine bisimine metal salt complex having an L 1 and/or L 2 independently can be an organylene group; alternatively, an organylene group consisting essentially of inert functional groups; or alternatively, a hydrocarbylene group.
  • the L 1 and/or L 2 organylene groups of a pyridine bisimine or pyridine bisimine first metal salt complex which have an L 1 and/or L 2 group independently can be a C 2 to C 20 , a C 2 to C 15 , a C 2 to C 10 , or a C 2 to C 5 organylene group.
  • the L 1 and/or L 2 organylene groups consisting essentially of inert functional groups of a pyridine bisimine or pyridine bisimine first metal salt complex which have an L 1 and/or L 2 group, independently can be a C 2 to C 2 o, a C 2 to Cu, a C 2 to Cjo, or a C 2 to C 5 organylene group consisting essentially of inert functional groups.
  • the L 1 and/or L 2 hydrocarbylene groups of a pyridine bisimine or pyridine bisimine first metal salt complex which have an L 1 and/or L 2 group independently can be a C 2 to C 20 , a C 2 to Ci 5 , a C 2 to Cm, or a C 2 to C 5 hydrocarbylene group.
  • the L 1 and/or L 2 hydrocarbylene groups of the pyridine bisimines and pyridine bisimine first metal salt complexes which have an L 1 and/or L 2 independently can be a C 2 to C 20 , a C 2 to Cm, or a C 2 to C 5 alkylene group.
  • L 1 and L 2 can be different; or alternatively, L 1 and L 2 can be the same.
  • L 1 and/or L 2 independently can have the structure -(C(R n ) 2 ) p -.
  • R 11 and p are independent features of L 1 and/or L 2 having the structure -(C(R n ) 2 ) p - and are independently described herein.
  • the independent descriptions of R 11 and p can be utilized without limitation, and in any combination, to describe L 1 and/or L 2 having the structure -(C(R n ) 2 ) p - and can be further utilized to describe the pyridine bisimines and/or the pyridine bisimine first metal salt complexes which have an L 1 and/or L 2 .
  • each R 11 independently can be hydrogen, an inert functional group, or a hydrocarbyl group; alternatively, hydrogen or a hydrocarbyl group; alternatively, hydrogen; alternatively, an inert functional group; or alternatively, a hydrocarbyl group.
  • General and specific inert functional groups and hydrocarbyl groups are independently described herein (e.g., as potential substituent groups) and these descriptions can be utilized without limitation to further describe L 1 and L 2 .
  • each p independently can be an integer from 1 to 5; alternatively, 2 or 3; alternatively, 2; or alternatively, 3.
  • L 1 and L 2 independently can be -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -C(CH 3 ) 2 -, or -CH 2 CH 2 CH 2 CH 2 -; alternatively, -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -; alternatively, -CH 2 CH 2 -; or alternatively, -CHCH 2 CH 2 -.
  • L 1 and L 2 can be different. In other aspects, L 1 and L 2 can be the same.
  • R 6 and/or R 7 of the pyridine bisimines and the pyridine bisimine first metal salt complexes independently can be an aryl group, a substituted aryl group, a phenyl group, or a substituted phenyl group; alternatively, an aryl group or a substituted aryl group; alternatively, a phenyl group or a substituted phenyl group; alternatively, an aryl group; alternatively, a substituted aryl group; alternatively, a phenyl group; or alternatively, a substituted phenyl group.
  • the R 6 and/or R 7 aryl groups of the pyridine bisimines and/or pyridine bisimine first metal salt complexes independently can be a C 6 to C 20 , a C 6 to C 15 , or a C 6 to C 10 aryl group.
  • the R 6 and/or R 7 substituted aryl groups of the pyridine bisimines and/or pyridine bisimine first metal salt complexes independently can be a C 6 to C 20 , a C 6 to C 15 , or a C 6 to C 10 substituted aryl group.
  • the R 6 and/or R 7 substituted phenyl groups of the pyridine bisimines and/or pyridine bisimine first metal salt complexes independently can be a C 6 to C 20 , a C 6 to C 15 , or a C 6 to C 15 substituted phenyl group.
  • Each substituent of a substituted aryl group (general or specific) or a substituted phenyl group (general or specific) which can be utilized as R 6 and/or R 7 can be a halide, an alkyl group, or a hydrocarboxy group; alternatively, a halide or an alkyl group; alternatively, a halide or a hydrocarboxy group; alternatively, an alkyl group or a hydrocarboxy group; alternatively, a halide; alternatively, an alkyl group; or alternatively, a hydrocarboxy group.
  • Halides, alkyl groups (general and specific), and hydrocarboxy groups (general and specific) that can be utilized as substituents are independently disclosed herein and can be utilized without limitation, and in any combination, to further describe R 6 and/or R 7 of the pyridine bisimines and the pyridine bisimine first metal salt complexes.
  • each substituted phenyl group which can be utilized as R 6 and/or R 7 of the pyridine bisimines and the pyridine bisimine first metal salt complexes independently can be a substituted phenyl group comprising a substituent at the 2- position, a substituted phenyl group comprising a substituent at the 3- position, a substituted phenyl group comprising a substituent at the 4- position, a substituted phenyl group comprising substituents at the 2- and 3- positions, a substituted phenyl group comprising substituents at the 2- and 4- positions, a substituted phenyl group comprising substituents at the 2- and 5- positions, a substituted phenyl group comprising substituents at the 3- and 5- positions, a substituted phenyl group comprising substituents at the 2- and 6- positions, or a substituted phenyl group comprising substituents at the 2-, 4-, and 6- positions; alternatively, a substituted phenyl group comprising a substituted
  • each substituted phenyl group which can be utilized as R 6 and/or R 7 of the pyridine bisimines and the pyridine bisimine first metal salt complexes independently can be selected such that (1) one, two, or three of the 2- and 6- positions of the R 6 and R 7 phenyl groups and/or substituted phenyl groups independently can be a halogen, a primary carbon atom group, or a secondary carbon atom group and the remainder of the 2- and 6- positions of the R 6 and R 7 phenyl groups and/or substituted phenyl groups can be hydrogen, (2) one of the 2- and 6- positions of the R 6 and R 7 phenyl groups and/or substituted phenyl groups can be a tertiary carbon atom group, none, one, or two of the 2- and 6- positions of the R 6 and R 7 phenyl groups and/or substituted phenyl groups independently can be a halogen, a primary carbon atom group or a secondary carbon atom group, and the remainder of
  • Each substituent of a substituted aryl group (general or specific) or a substituted phenyl group (general or specific) which can be utilized as R 6 and/or R 7 can be a halide, an alkyl group, or a hydrocarboxy group; alternatively, a halide or an alkyl group; alternatively, a halide or a hydrocarboxy group; alternatively, an alkyl group or a hydrocarboxy group; alternatively, a halide; alternatively, an alkyl group; or alternatively, a hydrocarboxy group.
  • Halides, alkyl groups (general and specific), and hydrocarboxy groups (general and specific) that can be utilized as substituents are independently disclosed herein and can be utilized without limitation, and in any combination, to further describe R 6 and/or R 7 of the pyridine bisimines and the pyridine bisimine first metal salt complexes.
  • substituted phenyl group(s) which meet the criteria for a substituted phenyl group (e.g., primary, secondary, tertiary, and quaternary carbon atom groups, among other criteria) and choose the appropriate substituted phenyl group(s) to meet any particular criteria for a substituted phenyl group(s) for a pyridine bisimine and/or a pyridine bisimine first metal salt described herein.
  • a substituted phenyl group e.g., primary, secondary, tertiary, and quaternary carbon atom groups, among other criteria
  • each substituted phenyl group which can be utilized as R 6 and/or R 7 of the pyridine bisimines and the pyridine bisimine first metal salt complexes independently can be a 2-substituted phenyl group, a 3 -substituted phenyl group, a 4-substituted phenyl group, a 2,3-disubstituted phenyl group, a 2,4-disubstituted phenyl group, a 2,5-disubstituted phenyl group, a 3,5-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group,
  • each substituted phenyl group which can be utilized as R 6 and/or R 7 of the pyridine bisimines and the pyridine bisimine first metal salt complexes independently can be selected such that (1) one, two, or three of the 2- and 6- positions of the R 6 and R 7 phenyl groups and/or substituted phenyl groups independently can be a halogen, a primary carbon atom group, or a secondary carbon atom group and the remainder of the 2- and 6- positions of the R 6 and R 7 phenyl groups and/or substituted phenyl groups can be hydrogen, (2) one of the 2- and 6- positions of the R 6 and R 7 phenyl groups and/or substituted phenyl groups can be a tertiary carbon atom group, none, one, or
  • Each substituent of a substituted aryl group (general or specific) or a substituted phenyl group (general or specific) which can be utilized as R 6 and/or R 7 can be a halide, an alkyl group, or a hydrocarboxy group; alternatively, a halide or an alkyl group; alternatively, a halide or a hydrocarboxy group; alternatively, an alkyl group or a hydrocarboxy group; alternatively, a halide; alternatively, an alkyl group; or alternatively, a hydrocarboxy group.
  • Halides, alkyl groups (general and specific), and hydrocarboxy groups (general and specific) that can be utilized as substituents are independently disclosed herein and can be utilized without limitation, and in any combination, to further describe R 6 and/or R 7 of the pyridine bisimines and the pyridine bisimine first metal salt complexes.
  • substituted phenyl group(s) which meet the criteria for a substituted phenyl group (e.g., primary, secondary, tertiary, and quaternary carbon atom groups, among other criteria) and choose the appropriate substituted phenyl group(s) to meet any particular criteria for a substituted phenyl group(s) for a pyridine bisimine and/or a pyridine bisimine first metal salt described herein.
  • a substituted phenyl group e.g., primary, secondary, tertiary, and quaternary carbon atom groups, among other criteria
  • R 6 and/or R 7 of the pyridine bisimines and the pyridine bisimine first metal salt complexes independently can be a phenyl group, a 2-methylphenyl group, a 2-ethylphenyl group, a 2- isopropylphenyl group, a 2-tert-butylphenyl group, a 2-(phenyl)phenyl group, a 2-trifluoromethylphenyl group, a 2-fluorophenyl group, a 2-methoxyphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-isopropylphenyl group, a 4-tert-butylphenyl group, a 4-fluorophenyl group, a 4- trifluoromethylphenyl group, a 4-methoxyphenyl group, a 2,3 -dimethyl phenyl group, a 2-fluoro-3- methylphenyl
  • R 6 and/or R 7 of the pyridine bisimines and the pyridine bisimine first metal salt complexes independently can be selected such that (1) one, two, or three of the 2- and 6- positions of the R 6 and R 7 phenyl groups and/or substituted phenyl groups independently can be a halogen, a primary carbon atom group, or a secondary carbon atom group and the remainder of the 2- and 6- positions of the R 6 and R 7 phenyl groups and/or substituted phenyl groups can be hydrogen, (2) one of the 2- and 6- positions of the R 6 and R 7 phenyl groups and/or substituted phenyl groups can be a tertiary carbon atom group, none, one, or two of the 2- and 6- positions of the R 6 and R 7 phenyl groups and/or substituted phenyl groups independently can be a halogen, a primary carbon atom group or a secondary carbon atom group, and the remainder of the 2- and 6- positions of the R 6 and R 7 phenyl groups
  • substituted phenyl group(s) which meet the criteria for a substituted phenyl group (e.g., primary, secondary, and tertiary carbon atom groups, among other criteria) and choose the appropriate substituted phenyl group(s) to meet any particular criteria for a substituted phenyl group(s) for a pyridine bisimine and/or a pyridine bisimine first metal salt described herein.
  • a substituted phenyl group e.g., primary, secondary, and tertiary carbon atom groups, among other criteria
  • the pyridine bisimine or the pyridine bisimine of the pyridine bisimine first metal salt complex can comprise, consist essentially of, or can be, a 2,6-bis[(aryl- imine)hydrocarbyl]pyridine, a bis [(substituted arylimine)hydrocarbyl]pyridine, or an [(arylimine)- hydrocarbyl], [(substituted arylimine)hydrocarbyl]pyridine; alternatively, a 2,6-bis[(arylimine)hydro- carbyljpyridine; alternatively, a bis[(substituted arylimine)hydrocarbyl]pyridine; or alternatively, an [(arylimine)hydrocarbyl], or a [(substituted arylimine)hydrocarbyl]pyridine.
  • the pyridine bisimine first metal salt complex can comprise, can consist essentially of, or can be, a 2,6- bis[(arylimine)hydrocarbyl]pyridine first metal salt complex, a bis [(substituted arylimine)hydro- carbyljpyridine first metal salt complex, or an [(arylimine)hydrocarbyl], [(substituted arylimine)- hydrocarbyljpyridine first metal salt complex; alternatively, a 2,6-bis[(arylimine)hydrocarbyl]pyridine first metal salt complex; alternatively, a bis [(substituted arylimine)hydrocarbyl]pyridine first metal salt complex; or alternatively, an [(arylimine)hydrocarbyl], [(substituted arylimine)hydrocarbyl]pyridine first metal salt complex.
  • the aryl groups of the 2,6-bis[(arylimine)hydrocarbyl]pyridine or the 2,6-bis[(arylimine)hydrocarbyl]pyridine first metal salt complex can be the same or can be different; alternatively, the same; or alternatively, different.
  • the substituted aryl groups of the 2,6- bis [(substituted arylimine)hydrocarbyl]pyridine or the 2,6-bis[(substituted arylimine)hydrocarbyl]pyridine first metal salt complex can be the same or can be different; alternatively, the same; or alternatively, different.
  • the pyridine bisimine or the pyridine bisimine of the pyridine bisimine first metal salt complex can comprise, consist essentially of, or can be, a 2,6-bis[(arylimine)hydrocarbyl]pyridine, a bis [(substituted arylimine)hydrocarbyl]pyridine, and/or an [(arylimine)hydrocarbyl], [(substituted arylimine)hydrocarbyl]pyridine wherein 1) one, two, or three of the aryl groups and/or substituted aryl groups positioned ortho to the carbon atom attached to the imine nitrogen independently can be a halogen, a primary carbon atom group, or a secondary carbon atom group and the remainder of the aryl groups and/or substituted aryl groups positioned ortho to the carbon atom attached to the imine nitrogen can be hydrogen, 2) one of the aryl groups and/or substituted aryl groups positioned ortho to the carbon atom attached to the imine nitrogen can be hydrogen,
  • Hydrocarbyl groups (general and specific), aryl groups (general and specific), and substituted aryl groups (general and specific) are independently described herein.
  • the independent descriptions of the hydrocarbyl group, aryl groups, and substituted aryl groups can be utilized without limitation, and in any combination, to further describe the 2,6- bis[(arylimine)hydrocarbyl]pyridine, the bis [(substituted arylimine)hydrocarbyl]pyridine, or the [(arylimine)hydrocarbyl], [(substituted arylimine)hydrocarbyl]pyridine which can be utilized as the pyridine bisimine or the pyridine bisimine first metal salt complex that can be utilized in the processes described herein.
  • aryl group(s) and/or substituted aryl group(s) which meet the criteria for aryl group and/or substituted aryl groups (e.g., primary, secondary, and tertiary carbon atom groups, among other criteria) and choose the appropriate aryl group(s) and/or substituted aryl group(s) to meet any particular criteria for the aryl group(s) and/or substituted phenyl group(s) for a pyridine bisimine and/or a pyridine bisimine first metal salt complex described herein.
  • aryl group(s) and/or substituted aryl group(s) which meet the criteria for aryl group and/or substituted aryl groups (e.g., primary, secondary, and tertiary carbon atom groups, among other criteria) and choose the appropriate aryl group(s) and/or substituted aryl group(s) to meet any particular criteria for the aryl group(s) and/or substituted phenyl group(s)
  • the pyridine bisimine and/or the pyridine bisimine of the pyridine bisimine first metal salt complex can be 2,6-bis[(phenylimine)methyl]pyridine, 2,6-bis[(2-methylphenyl- imine)methyl]pyridine, 2,6-bis[(2-ethylphenylimine)methyl]pyridine, 2,6-bis[(2-isopropylphenylimine)- methyl] pyridine, 2,64jis[(2,4-dimethylphenylimine)methyl]pyridine, 2,6-bis[(2,6-diethylphenylimine)- methyl] pyridine, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)methyl]pyridine, 2- [(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridine, or 2-[(2,4,6- trimethylphenylimine)methyl]
  • a phenanthroline imine (which also can be referred to as a 1 , 10-phenanthroline-2-imine or a 2-iminyl- 1 , 10-phenanthroline) and a metal salt, or a phenanthroline imine first metal salt complex (which also can be referred to as a 1 , 10-phenanthroline-2-imine first metal salt complex or a 2-iminyl- 1 , 10-phenanthroline first metal salt complex) can be utilized in the processes described herein.
  • the phenanthroline imine, or the phenanthroline imine of the phenanthroline imine first metal salt complex can be any phenanthroline imine, or any phenanthroline imine of the phenanthroline imine first metal salt complex, that when contacted with the other materials of the process described herein (e.g., metal salt, ethylene, organoaluminum compound and/or any other appropriate reagent(s)), under the appropriate conditions, can form an oligomer product.
  • the other materials of the process described herein e.g., metal salt, ethylene, organoaluminum compound and/or any other appropriate reagent(s)
  • the phenanthroline imine and the metal salt, or the phenanthroline imine first metal salt complex are independent elements of the processes described herein and are independently disclosed herein.
  • the independent descriptions of the phenanthroline imine and the metal salt, or the phenanthroline imine first metal salt complex (or the phenanthroline imine and the first metal salt of the phenanthroline imine first metal salt complex) can be used without limitation, and in any combination, to further describe the processes that can be utilized in the aspects and/or embodiments of the processes described herein.
  • the phenanthroline imine can have Structure PTI I.
  • the phenanthroline imine first metal salt com lex can have Structure PTIMC I.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 of the phenanthroline imine having Structure PTI I or phenanthroline imine first metal salt complex having Structure PTIMC I are independent elements of the phenanthroline imine having Structure PTI I and the phenanthroline imine first metal salt complex having Structure PBIMC I and are independently described herein.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 can be utilized without limitation, and in any combination, to further describe the phenanthroline imine having Structure PTI I and/or the phenanthroline imine first metal salt complex having Structure PBIMC I.
  • the first metal salt, MX n is independently described herein and can be combined, without limitation, with the independently described R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 to further describe the phenanthroline imine first metal salt complex structures described herein.
  • R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 of the phenanthroline imines and phenanthroline imine first metal salt complexes independently can be hydrogen, an inert functional group, or an organyl group; alternatively, hydrogen or an organyl group; alternatively, an inert functional group or an organyl group; alternatively, hydrogen, an inert functional group, or an organyl group consisting essentially of inert functional groups; alternatively, hydrogen or an organyl group consisting essentially of inert functional groups; alternatively, an inert functional group or an organyl group consisting essentially of inert functional groups; alternatively, hydrogen, an inert functional group, or a hydrocarbyl group; alternatively, hydrogen or a hydrocarbyl group; alternatively, an inert functional group or a hydrocarbyl group; alternatively, hydrogen or an inert functional group or a hydrocarbyl group; alternatively, hydrogen or an inert functional
  • the organyl groups which can be utilized as R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and/or R 19 independently can be a Ci to C 20 , a Ci to Ci 5 , a Ci to Cm, or a Ci to C 5 organyl group.
  • the organyl groups consisting essentially of inert functional groups which can be utilized as R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and/or R 19 independently can be a C x to C 20 , a C x to C 15 , a C x to C 10 , or a C x to C 5 organyl group consisting essentially of inert functional groups.
  • the hydrocarbyl groups which can be utilized as R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 independently can be a Q to C 2 o, a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 hydrocarbyl group.
  • the inert functional groups which can be utilized as R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 independently can be a halide or an alkoxy group; alternatively, a halide; or alternatively, an alkoxy group.
  • the hydrocarbyl group which can be utilized as R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and/or R 19 of the phenanthroline imines and phenanthroline imine first metal salt complexes which have an R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and/or R 19 group, independently can be a Ci to C 20 , a Ci to Cio, or a Ci to C 5 .
  • the alkyl groups which can be utilized as R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and/or R 19 of the phenanthroline imines and phenanthroline imine first metal salt complexes which have an R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and/or R 19 group, independently can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group.
  • the R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and/or R 19 alkyl groups of the phenanthroline imines and phenanthroline imine first metal salt complexes which have an R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and/or R 19 alkyl group, independently can be a methyl group, an ethyl group, an iso-propyl (2-propyl) group, a tert-butyl (2-methyl-2 -propyl) group, or a neopentyl (2,2-dimethyl-l -propyl) group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, a n-propyl (1 -propyl) group; alternatively, an iso-propyl (2- propyl) group; alternatively, a tert-butyl (2-methyl-2 -propy
  • each halide which can be utilized as R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and/or R 19 of the phenanthroline imines and phenanthroline imine first metal salt complexes independently can be fluoride, chloride, bromide or iodide; alternatively, fluoride, chloride, or bromide; alternatively, fluoride; alternatively, chloride; or alternatively, bromide.
  • each alkoxy group which can be utilized as R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and/or R 19 of the phenanthroline imines and phenanthroline imine first metal salt complexes independently can be a Ci to Cio alkoxy group or a Ci to C 5 alkoxy group.
  • each alkoxy group which can be utilized as R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 independently can be a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n- pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a 2-methyl- 1 -butoxy group, a tert-pentoxy group, a 3 -methyl- 1 -butoxy group, a 3-methyl-2-butoxy group, or a neo-pentoxy group; alternatively, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, or a neo-pentoxy group; alternatively, a methoxy group; alternatively, an ethoxy group,
  • R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 of the phenanthroline imine each can be hydrogen.
  • the phenanthroline imine can have Structure PTI II.
  • R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 of the phenanthroline imine first metal salt complex each can be hydrogen.
  • the phenanthroline imine first metal salt complex can have Structure PTIMC II.
  • R 11 and R 12 of the phenanthroline imine having Structure PTI I or Structure PTI II or the phenanthroline imine first metal salt complex having Structure PTIMC I or Structure PTIMC II are independent elements of the phenanthroline imine having Structure PTI I or Structure PTI II and the phenanthroline imine first metal salt complex having Structure PTIMC I or Structure PTIMC II and are independently described herein.
  • the independent descriptions of R 11 and R 12 can be utilized without limitation, and in any combination, to further describe the phenanthroline imine having Structure PTI I or Structure PTI II and/or the phenanthroline imine first metal salt complex having Structure PTIMC I or Structure PTIMC II.
  • the metal salt, MX n is independently described herein can be combined, without limitation, with the independently described R 11 and R 12 to further describe the phenanthroline imine first metal salt complex having Structure PTIMC I or Structure PTIMC II.
  • R 11 of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be an aryl group, a substituted aryl group, a phenyl group, or a substituted phenyl group; alternatively, an aryl group or a substituted aryl group; alternatively, a phenyl group or a substituted phenyl group; alternatively, an aryl group; alternatively, a substituted aryl group; alternatively, a phenyl group; or alternatively, a substituted phenyl group.
  • the R 11 aryl group of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a C 6 to C 2 o, a C 6 to Ci 5 , or a C 6 to Cm aryl group.
  • the R 11 substituted aryl groups of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a C 6 to C 2 o, a C 6 to Ci 5 , or a C 6 to Cm substituted aryl group.
  • the R 11 substituted phenyl groups of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a C 6 to C 2 o, a C 6 to Ci 5 , or a C 6 to Ci 5 substituted phenyl group.
  • Each substituent of a substituted aryl group (general or specific) or a substituted phenyl group (general or specific) which can be utilized as R 11 can be a halide, an alkyl group, or a hydrocarboxy group; alternatively, a halide or an alkyl group; alternatively, a halide or a hydrocarboxy group; alternatively, an alkyl group or a hydrocarboxy group; alternatively, a halide; alternatively, an alkyl group; or alternatively, a hydrocarboxy group.
  • Halides, alkyl groups (general and specific), and hydrocarboxy groups (general and specific) that can be utilized as substituents are independently disclosed herein and can be utilized without limitation, and in any combination, to further describe R 11 of the phenanthroline imines and the phenanthroline imine first metal salt complexes.
  • each substituted phenyl group which can be utilized as R 11 substituted phenyl groups of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a substituted phenyl group comprising a substituent at the 2- position, a substituted phenyl group comprising a substituent at the 3- position, a substituted phenyl group comprising a substituent at the 4- position, a disubstituted phenyl group comprising substituents at the 2- and 3- positions, a disubstituted phenyl group comprising substituents at the 2- and 4- positions, a disubstituted phenyl group comprising substituents at the 2- and 5- positions, a disubstituted phenyl group comprising substituents at the 3- and 5- positions, a disubstituted phenyl group comprising substituents at the 2- and 6- positions, or a trisubstituted phenyl group
  • each substituted phenyl group which can be utilized as R 11 substituted phenyl groups of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a 2-substituted phenyl group, a 3 -substituted phenyl group, a 4-substituted phenyl group, a 2,3 -disubstituted phenyl group, a 2,4-disubstituted phenyl group, a 2,5 -disubstituted phenyl group, a 3,5-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group,
  • substituted phenyl group has more than one substituent, two or more of the substituents can be different, each substituent can be different, or each substituent can be the same; alternatively, two or more of the substituents can be different; alternatively, each substituent can be different; or alternatively, each substituent can be the same.
  • Each substituent of a substituted phenyl group which can be utilized as R 11 independently can be a halide, an alkyl group, or a hydrocarboxy group; alternatively, a halide or an alkyl group; alternatively, a halide or a hydrocarboxy group; alternatively, an alkyl group or a hydrocarboxy group; alternatively, a halide; alternatively, an alkyl group; or alternatively, a hydrocarboxy group.
  • Halides, alkyl groups (general and specific), and hydrocarboxy groups (general and specific) that can be utilized as substituents are independently disclosed herein and can be utilized without limitation, and in any combination, to further describe R 11 of the phenanthroline imines and the phenanthroline imine first metal salt complexes.
  • each substituted phenyl group which can be utilized as an R 11 substituted phenyl group of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a substituted phenyl group comprising an alkyl group at the 2- position, a substituted phenyl group comprising an alkyl group at the 4- position, a disubstituted phenyl group comprising alkyl groups at the 2- and 4- positions, a disubstituted phenyl group comprising alkyl groups at the 2- and 6- positions, a trisubstituted phenyl group comprising alkyl groups at the 2-, 4-, and 6- positions, a substituted phenyl group comprising a halide at the 2- position, a disubstituted phenyl group comprising halides at the 2- and 4- positions, or a trisubstituted phenyl group comprising halides at the 2-, 4-, and 6- positions;
  • each substituted phenyl group which can be utilized as an R 11 substituted phenyl group of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a 2-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, a 2,4,6-trialkylphenyl group, a 2-halophenyl group, a 2,4-dihalophenyl group, a 2,4,6-trihalophenyl group, a 2,6-dialkyl-4-halophenyl group, or a 2,6-dihalo-4-alkylphenyl group; alternatively, a 2-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphen
  • substituted phenyl group has more than one substituent
  • two or more of the substituents can be different, each substituent can be different, or each substituent can be the same; alternatively, two or more of the substituents can be different; alternatively, each substituent can be different; or alternatively, each substituent can be the same.
  • Halides and alkyl groups (general and specific) that can be utilized as substituents are independently disclosed herein and can be utilized without limitation, and in any combination, to further describe R 11 of the phenanthroline imines and the phenanthroline imine first metal salt complexes.
  • the substituted phenyl R 11 group of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a 2-methylphenyl group, a 2-ethylphenyl group, a 2-isopropylphenyl group, a 2-tert-butylphenyl group, a 2-fluorophenyl group, a 2-chlorophenyl group, a 2-bromophenyl group, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a 2,6-diisopropylphenyl group, a 2,6-di-tert-butylphenyl group, a 2,4,6-trimethylphenyl group, a 2,6-difluorophenyl group, a 2,6- dichlorophenyl group, a 2,6-dibromophenyl group, a 2,4,6-trifluorophen
  • R 12 of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be hydrogen or an organyl group; alternatively, hydrogen or an organyl group consisting essentially of inert functional groups; alternatively, hydrogen or a hydrocarbyl group; alternatively, hydrogen; alternatively, an organyl group; alternatively, an organyl group consisting essentially of inert functional groups; or alternatively, a hydrocarbyl group.
  • the R 12 organyl groups of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a Ci to C 20 , a Ci to Ci 5 , a Ci to Cm, or a Ci to C 5 organyl group.
  • the R 12 organyl groups consisting essentially of inert functional groups, of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a Ci to C 2 o, a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 organyl group consisting essentially of inert functional groups.
  • the R 12 hydrocarbyl groups of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a Q to C 2 o, a Ci to C 15 , a Ci to C 10 , or a Ci to C 5 hydrocarbyl group.
  • the R 12 hydrocarbyl group of any phenanthroline imine and any phenanthroline imine first metal salt complex described herein can be an alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a substituted aralkyl group.
  • the R 12 hydrocarbyl group of any phenanthroline imine and any phenanthroline imine first metal salt complex described herein can be an alkyl group; alternatively, a cycloalkyl group or a substituted cycloalkyl group; alternatively, an aryl group or a substituted aryl group; alternatively, an aralkyl group or a substituted aralkyl group; or alternatively, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
  • the R 12 hydrocarbyl group of any phenanthroline imine and any phenanthroline imine first metal salt complex described herein can be an alkyl group; alternatively, a cycloalkyl group; alternatively, a substituted cycloalkyl group; alternatively, an aryl group; alternatively, a substituted aryl group; alternatively, an aralkyl group; or alternatively, a substituted aralkyl group.
  • each alkyl group which can be utilized as R 12 of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a Ci to C 2 o, a Ci to C 10 , or a Ci to C 5 alkyl group.
  • each cycloalkyl group which can be utilized as R 12 of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a C 4 to C 20 , a C 4 to C 15 , or a C 4 to C 10 cycloalkyl group.
  • each substituted cycloalkyl group which can be utilized as R 12 can be a C 4 to C 20 , a C 4 to C 15 , or a C 4 to C 10 substituted cycloalkyl group.
  • each aryl group which can be utilized as R 12 of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a C 6 to C 20 , a C 6 to C 15 , or a C 6 to C 10 aryl group.
  • each substituted aryl group which can be utilized as R 12 can be a C 6 to C 20 , a C 6 to C 15 , or a C 6 to C 10 substituted aryl group.
  • each aralkyl group which can be utilized R 12 of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a C 7 to C 20 , a C 7 to Ci5, or a C 7 to Cm aralkyl group.
  • each substituted aralkyl group which can be utilized as R 12 of the phenanthroline imines and the phenanthroline imine first metal salt complexes can be a C 7 to C 2 o, a C 7 to Ci 5 , or a C 7 to Cm substituted aralkyl group.
  • Each substituent of a substituted alkyl group (general or specific), a substituted cycloalkyl group (general or specific), a substituted aryl group (general or specific), and/or a substituted aralkyl group (general or specific) can be a hydrocarbyl group.
  • Substituent hydrocarbyl groups are independently disclosed herein.
  • substituent hydrocarbyl groups can be utilized without limitation to further describe the substituted cycloalkyl groups, the substituted aryl groups, or the substituted aralkyl groups which can be utilized as R 12 of the phenanthroline imines and the phenanthroline imine first metal salt complexes.
  • R 12 of any phenanthroline imine and any phenanthroline imine first metal salt complex described herein can be hydrogen, a methyl group, an ethyl group, an n-propyl (1 -propyl) group, an iso-propyl (2-propyl) group, a tert-butyl (2-methyl-2-propyl) group, a neopentyl (2,2-dimethyl-l -propyl) group, or a phenyl group; alternatively, hydrogen, a methyl group, an ethyl group, an n-propyl ( 1 -propyl) group, an iso-propyl (2-propyl) group, or a phenyl group; alternatively, a methyl group, an ethyl group, an n-propyl ( 1 -propyl) group, or an iso-propyl (2-propyl) group; alternatively,
  • the phenanthroline imine or the phenanthroline imine of the phenanthroline imine first metal salt complex can comprise, can consist essentially of, or can be, a 2-(hydrocarbylimine)- 1 , 10-phenanthroline, a 2-[(hydrocarbylimine)hydrocarbyl]-l , 10-phenanthroline, a 2-(arylimine)-l , 10- phenanthroline, a 2-[(arylimine)hydrocarbyl]- 1 , 10-phenanthroline, a 2-(substituted arylimine)-l , 10- phenanthroline, or a 2-[(substituted arylimine)hydrocarbyl]- 1 , 10-phenanthroline; alternatively, a 2- (hydrocarbylimine)- 1 , 10-phenanthroline; alternatively, a 2- [(hydrocarbylimine)hydrocarbyl] -1 , 10- phenanthro
  • the phenanthroline imine or the phenanthroline imine of the phenanthroline imine first metal salt complex can comprise, can consist essentially of, or can be, a 2-(2,6-disubstituted phenylimine)- 1 , 10-phenanthroline, a 2-[(2,6-disubstituted phenylimine)alkyl]- 1 , 10-phenanthroline, a 2- [(2,6-disubstituted phenylimine)phenyl]- 1 , 10-phenanthroline, a 2-(2,4,6-trisubstituted phenylimine)- 1 , 10- phenanthroline, a 2-[(2,4,6-trisubstituted phenylimine)alkyl]- 1 , 10-phenanthroline, or a 2-[(2,4,6- trisubstituted phenylimine)phenyl]- 1 , 10-phenanthroline; alternatively
  • Each substituent of a 2-(2,6-disubstituted phenylimine)- 1, 10- phenanthroline, a 2-[(2,6-disubstituted phenylimine)alkyl]- 1,10-phenanthroline, a 2-[(2,6-disubstituted phenylimine)phenyl]- 1,10-phenanthroline, a 2-(2,4,6-trisubstituted phenylimine)- 1, 10-phenanthroline, a 2-[(2,4,6-trisubstituted phenylimine)alkyl]- 1, 10-phenanthroline, or a 2-[(2,4,6-trisubstituted phenylimine)phenyl]- 1,10-phenanthroline can be an alkyl group or a halo group; alternatively, an alkyl group; or alternatively, a halo group.
  • Substituent alkyl groups (general and specific) and halo group are independently disclosed herein. These substituent alkyl groups and halo groups can be utilized without limitation to further describe the substituents of the phenanthroline imines or the phenanthroline imines of the phenanthroline imine first metal salt complexes.
  • the phenanthroline imine or the phenanthroline imine of the phenanthroline imine first metal salt complex can comprise, can consist essentially of, or can be, a 2-(2,6- dialkylphenylimine)- 1,10-phenanthroline, a 2-[(2,6-dialkylphenylimine)alkyl]- 1, 10-phenanthroline, a 2- [(2,6-dialkylphenylimine)phenyl]- 1 , 10-phenanthroline, a 2-(2,4,6-trialkylphenylimine)- 1 , 10-phenanthroline, a 2- [(2,4,6-trialkylphenylimine)alkyl]- 1, 10-phenanthroline, a 2-[(2,4,6-trialkylphenyl- imine)phenyl]- 1,10-phenanthroline, a 2-(2,6-dihalophenylimine)- 1,10-phenanthroline, a 2-[(2,6-dialkylphenylim
  • Substituent alkyl groups (general and specific) and halo groups are independently disclosed herein. These substituent alkyl groups and halo groups can be utilized without limitation to further describe the substituents of the phenanthroline imines or the phenanthroline imines of the phenanthroline imine first metal salt complexes.
  • the phenanthroline imine or the phenanthroline imine of the phenanthroline imine first metal salt complex can comprise, can consist essentially of, or can be, 2-(2,6- difluorophenylimine)- 1 , 10-phenanthroline, 2-(2,6-dichlorophenylimine)- 1 , 10-phenanthroline, 2-(2,6- dibromophenylimine)- 1 , 10-phenanthroline, 2-(2,6-dimethylphenylimine)- 1 , 10-phenanthroline, 2-(2,6- diethylphenylimine)- 1 , 10-phenanthroline, 2-(2,6-diisopropylphenylimine)- 1 , 10-phenanthroline, 2-[(2,6- difluorophenylimine)methyl]- 1 , 10-phenanthroline, 2-[(2,6-dichlorophenylimine)methyl] -1, 10-phenanthroline, 2-
  • the processes described herein can utilize a metal salt, a first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt disclosed herein), and/or a second metal salt.
  • a metal salt, a first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt disclosed herein), and/or a second metal salt the metal salt, first metal salt, and second metal salt are independent of each other and can be the same or different: alternatively, the same; or alternatively different.
  • the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt disclosed herein), and/or the second metal salt can have the formula MX n .
  • MX n within the formula of the metal salt having the formula MX n (whether it is the metal salt, the first metal salt, and/or a second metal salt), M represents the metal atom, X represents a monoanionic species, and n represents the number of monoanionic species (or the metal oxidation state).
  • the metal, the monoanionic species, X, and the number of anionic species (or the metal oxidation state), n are independent elements of the metal salt (whether it is the metal salt, the first metal salt, and/or a second metal salt) and are independently described herein.
  • the metal salt having the formula MX n (whether it is the metal salt, the first metal salt, and/or the second metal salt) can be described utilizing any aspect and/or embodiment of the metal described herein, any aspect or embodiment of the monoanionic specie described herein, and any aspect and/or embodiment of the number of monoanionic species (or metal oxidation state) described herein.
  • the metal of the metal salt (whether it is the metal salt, the first metal salt, and/or the second metal salt) independently can be a group 8 or group 9 metal; alternatively, a group 8 metal; or alternatively, a group 9 metal.
  • metal of the metal salt which can be utilized as the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be iron (Fe) or cobalt (Co); alternatively, iron (Fe); or alternatively, cobalt (Co).
  • the oxidation state of the metal of the metal salt and/or number, n, of monoanionic species, X, of the metal salt which can be utilized as the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described), and/or the second metal salt independently can be any positive integer that corresponds to an oxidation state available to the metal atom.
  • the oxidation state of the metal of the metal salt and/or number, n, of monoanionic species, X, of the metal salt which can be utilized as the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be 1, 2 or 3; alternatively, 2 or 3; alternatively, 1 ; alternatively, 2; or alternatively, 3.
  • the monoanionic specie, X, of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be any monoanionic specie.
  • the monoanionic specie, X can be a halide, a carboxylate, a ⁇ -diketonate, a hydrocarboxide, a nitrate, or a chlorate; alternatively, a halide, a carboxylate, a ⁇ -diketonate, or a hydrocarboxide; or alternatively, a halide, a carboxylate, or a ⁇ -diketonate.
  • the hydrocarboxide can be an alkoxide, an aryloxide, or an aralkoxide.
  • hydrocarboxides (and subdivisions of hydrocarboxide) are the anion analogues of the hydrocarboxy group.
  • the monoanionic specie, X, of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be a halide, a carboxylate, a ⁇ -diketonate, or an alkoxide; alternatively, a carboxylate; alternatively, a ⁇ -diketonate; alternatively, a hydrocarboxide; alternatively, an alkoxide; or alternatively, an aryloxide.
  • each halide monoanionic specie, X, of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be fluorine, chlorine, bromine, or iodine; or alternatively, chlorine, bromine, or iodine.
  • each halide monoanionic specie, X, of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be chlorine; alternatively, bromine; or alternatively, iodine.
  • each carboxylate monoanionic specie, X, of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be a Ci to C 2 o or a Ci to Cm carboxylate.
  • each carboxylate of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be acetate, a propionate, a butyrate, a pentanoate, a hexanoate, a heptanoate, an octanoate, a nonanoate, a decanoate, an undecanoate, or a dodecanoate; or alternatively, a pentanoate, a hexanoate, a heptanoate, an octanoate, a nonanoate, or a decanoate.
  • each carboxylate monoanionic specie, X, of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be acetate, propionate, n-butyrate, valerate (n-pentanoate), neo-pentanoate, capronate (n-hexanoate), n-heptanoate, caprylate (n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate (n-decanoate), n-undecanoate, or laurate (n-dodecanoate); alternatively, valerate (n-pentanoate), neo-pentanoate, capronate (n-hexanoate), n- heptanoate, caprylate (n--pent
  • each ⁇ -diketonate monoanionic specie, X, of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be a Ci to C 2 o or a Ci to Cm ⁇ -diketonate.
  • each ⁇ -diketonate monoanionic specie, X, of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be acetylacetonate (i.e., 2,4-pentanedionate), hexafluoroacetylacetonate (i.e., l , l , l ,5,5,5-hexafluoro-2,4-pentanedionate), or benzoylacetonate; alternatively, acetylacetonate; alternatively, hexafluoroacetylacetone; or alternatively, benzoylacetonate .
  • acetylacetonate i.e., 2,4-pentanedionate
  • hexafluoroacetylacetonate i.e., l
  • each hydrocarboxide monoanionic specie, X, of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be any Ci to C 2 o or Ci to Cm hydrocarboxide.
  • each hydrocarboxide monoanionic specie, X, of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be a Ci to C 2 o alkoxide; alternatively, a Ci to Cm alkoxide; alternatively, a C 6 to C 2 o aryloxide; or alternatively, a C 6 to Cio aryloxide.
  • each alkoxide monoanionic specie, X, of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be methoxide, ethoxide, a propoxide, or a butoxide.
  • each alkoxide monoanionic specie, X, of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be methoxide, ethoxide, isopropoxide, or tert-but oxide; alternatively, methoxide; alternatively, an ethoxide; alternatively, an iso-propoxide; or alternatively, a tert-but oxide.
  • each aryloxide monoanionic specie, X, of the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can be phenoxide.
  • the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can comprise, can consist essentially of, or can be an iron salt, a cobalt salt, or a combination thereof; alternatively, an iron salt; or alternatively, a cobalt salt.
  • the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can comprise, can consist essentially of, or can be an iron halide, a cobalt halide, an iron ⁇ -diketonate, a cobalt ⁇ -diketonate, an iron carboxylate, a cobalt carboxylate or any combination thereof; alternatively, an iron halide, an iron ⁇ -diketonate, an iron carboxylate, or any combination thereof; or alternatively, an cobalt halide, an cobalt ⁇ -diketonate, an cobalt carboxylate, or any combination thereof.
  • the metal salt, the first metal salt (as a part of any heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt described herein), and/or the second metal salt independently can comprise, can consist essentially of, or can be, iron(II) fluoride, cobalt(II) fluoride, iron(III) fluoride, cobalt(III) fluoride, iron(II) bromide, cobalt(II) bromide, iron(III) bromide, cobalt(III) bromide, iron(II) iodide, cobalt(II) iodide, iron(III) iodide, cobalt(III) iodide, iron(II) acetate, cobalt(II) acetate, iron(III) acetate, iron(III) acetate, iron(II) acetylacetonate, cobalt(II) acet
  • the heteroatomic ligand metal salt complex comprising a heteroatomic ligand compl
  • the heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt can be selected from the group consisting of 2,6-bis[(phenylimine) methyl] pyridine iron dichloride, 2,6-bis[(2-methylphenylimine)methyl]pyridine iron dichloride, 2,6- bis [(2-ethylphenylimine)methyl]pyridine iron dichloride, 2,6-bis [(2-isopropylphenylimine)methyl] - pyridine iron dichloride, 2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine iron dichloride, 2,6-bis[(2,6- diethylphenylimine)methyl]pyridine iron dichloride, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4- methylphenylimine)methyl]pyridine iron dichloride, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5- dimethyl
  • the heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt can be selected from the group consisting of 2-[(2,6-difluorophenylimine)-l,10-phenanthroline iron dichloride, 2-[(2,6- dichlorophenylimine)-l, 10-phenanthroline iron dichloride, 2-[(2,6-dibromophenylimine)-l,10- phenanthroline iron dichloride, 2-[(2,6-dimethylphenylimine)-l, 10-phenanthroline iron dichloride, 2- [(2,6-diethylphenylimine)- 1 , 10-phenanthroline iron dichloride, 2-[(2,6-diisopropylphenylimine)- 1, 10- phenanthroline iron dichloride, 2- [(2,6-difluorophenylimine)methyl]- 1, 10-phenanthroline iron dichloride, 2-[(2,6-dichlor
  • the metal salt, the heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt), and/or the second metal salt can further comprise a neutral ligand.
  • the neutral ligand is not provided in the names, structures, or formulas provided herein, it should be understood that the metal salt, the heteroatomic ligand metal salt complex (comprising a heteroatomic ligand complexed to a first metal salt), and/or the second metal salt names and depictions do not limit the metal salt, the heteroatomic ligand metal salt complex (comprising a heteroatomic ligand complexed to a first metal salt), and/or the second metal salt names and depictions to those not having a neutral ligand.
  • the metal salt, the heteroatomic ligand metal salt complex (comprising a heteroatomic ligand complexed to a first metal salt), and/or the second metal salt which can be utilized in any aspect disclosed herein or any embodiment disclosed herein can include a neutral ligand and that these names and depictions provided herein do not limit the metal salt, the heteroatomic ligand metal salt complex (comprising a heteroatomic ligand complexed to a first metal salt), and/or the second metal salt to those which do not comprise a neutral ligand regardless of the language utilized to describe the metal salts or metal salt complexes.
  • Neutral ligands are provided herein and can be utilized without limitation to further describe the metal salt, the heteroatomic ligand metal salt complex (comprising a heteroatomic ligand complexed to a first metal salt), and/or the second metal salt.
  • the neutral ligand can be any neutral ligand that forms an isolatable compound with the metal salt, the heteroatomic ligand metal salt complex (comprising a heteroatomic ligand complexed to a first metal salt), and/or the second metal salt.
  • each neutral ligand independently can be a nitrile, an ether, or an amine; alternatively, a nitrile; alternatively, an ether; or alternatively, an amine.
  • the number of neutral ligands of the metal salt, the heteroatomic ligand metal salt complex (comprising a heteroatomic ligand complexed to a first metal salt), and/or the second metal salt can be any number that forms an isolatable compound with the metal salt and/or the heteroatomic ligand metal salt complex.
  • the number of neutral ligands of the metal salt, the heteroatomic ligand metal salt complex (comprising a heteroatomic ligand complexed to a first metal salt), and/or the second metal salt can be 1, 2, 3, 4, 5, or 6; alternatively, 1 ; alternatively, 2; alternatively, 3; alternatively, 4; alternatively, 5; or alternatively, 6.
  • each nitrile ligand which can be utilized as the neutral ligand independently can be a C 2 to C 20 nitrile; or alternatively, a C 2 to Ci 0 nitrile.
  • each nitrile ligand independently can be a C 2 to C 20 aliphatic nitrile, a C 7 to C 20 aromatic nitrile, a C 8 to C 20 aralkane nitrile, or any combination thereof; alternatively, a C 2 to C 20 aliphatic nitrile; alternatively, a C 7 to C 20 aromatic nitrile; or alternatively, a C 8 to C 20 aralkane nitrile.
  • each nitrile ligand independently can be a C 2 to C 10 aliphatic nitrile, a C 7 to C 10 aromatic nitrile, a C 8 to C 10 aralkane nitrile, or any combination thereof; alternatively, a Ci to C 10 aliphatic nitrile; alternatively, a C 7 to C 10 aromatic nitrile; or alternatively, a C 8 to C 10 aralkane nitrile.
  • each aliphatic nitrile independently can be acetonitrile, propionitrile, a butyronitrile, benzonitrile, or any combination thereof; alternatively, acetonitrile; alternatively, propionitrile; alternatively, a butyronitrile; or alternatively, benzonitrile.
  • each ether ligand which can be utilized as the neutral ligand independently can be a C 2 to C 40 ether; alternatively, a C 2 to C 30 ether; or alternatively, a C 2 to C 20 ether.
  • each ether ligand independently can be a C 2 to C 40 aliphatic ether, a C 3 to C 40 aliphatic cyclic ether, a C 4 to C 0 aromatic cyclic ether; alternatively, a C 2 to C 0 aliphatic acyclic ether or a C 3 to C 0 aliphatic cyclic ether; alternatively, a C 2 to C 0 aliphatic acyclic ether; alternatively, a C 3 to C 0 aliphatic cyclic ether; or alternatively, a C to C 0 aromatic cyclic ether.
  • each ether ligand independently can be a C 2 to C 30 aliphatic ether, a C 3 to C 30 aliphatic cyclic ether, a C to C 30 aromatic cyclic ether; alternatively, a C 2 to C 30 aliphatic acyclic ether or a C 3 to C 30 aliphatic cyclic ether; alternatively, a C 2 to C 30 aliphatic acyclic ether; alternatively, a C 3 to C 30 aliphatic cyclic ether; or alternatively, a C to C 30 aromatic cyclic ether.
  • each ether ligand independently can be a C 2 to C 20 aliphatic ether, a C to C 20 aliphatic cyclic ether, a C 4 to C 20 aromatic cyclic ether; alternatively, a C 2 to C 20 aliphatic acyclic ether or a C to C 20 aliphatic cyclic ether; alternatively, a C 2 to C 20 aliphatic acyclic ether; alternatively, a C to C 20 aliphatic cyclic ether; or alternatively, a C 4 to C 20 aromatic cyclic ether.
  • each ether ligand independently can be dimethyl ether, diethyl ether, a dipropyl ether, a dibutyl ether, methyl ethyl ether, a methyl propyl ether, a methyl butyl ether, tetrahydrofuran, a dihydrofuran, 1,3-dioxolane, tetrahydropyran, a dihydropyran, a pyran, a dioxane, furan, benzofuran, isobenzofuran, isobenzofuran, dibenzofuran, diphenyl ether, a ditolyl ether, or any combination thereof; alternatively, dimethyl ether, diethyl ether, a dipropyl ether, a dibutyl ether, methyl ethyl ether, a methyl propyl ether, a methyl butyl ether, or any combination thereof; alternatively, te
  • each amine ligand which can be utilized as the ⁇ - ⁇ -diimine neutral ligand independently can be a monohydrocarbylamine, a dihydrocarbylamine, a trihydrocarbylamine, or any combination thereof; alternatively, a monohydrocarbylamine; alternatively, a dihydrocarbylamine; or alternatively, a trihydrocarbylamine.
  • Monohydrocarbylamines which can be utilized as the non-a-diimine neutral ligand can be a Q to C 30 monohydrocarbylamine, a Ci to C 20 monohydrocarbylamine, a Q to C 10 monohydrocarbylamine, or a Ci to C 5 monohydrocarbylamine.
  • Dihydrocarbylamines which can be utilized as the ⁇ - ⁇ -diimine neutral ligand can be a C 2 to C 30 dihydrocarbylamine, a C 2 to C 2 o dihydrocarbylamine, a C 2 to Cio dihydrocarbylamine, or a C 2 to C 5 dihydrocarbylamine.
  • Trihydrocarbylamines which can be utilized as the ⁇ - ⁇ -diimine neutral ligand can be a C 3 to C 30 trihydrocarbylamine, a C 3 to C 20 trihydrocarbylamine, or a C 3 to Cio trihydrocarbylamine.
  • Hydrocarbyl groups (general and specific) are disclosed herein (e.g., as substituent groups, among other places) and can be utilized without limitation to further describe the monohydrocarbylamines, dihydrocarbylamines, and/or trihydrocarbylamines which can be utilized as the neutral ligand.
  • each hydrocarbyl group of the dihydrocarbylamine is independent of each other and can be the same: or alternatively, can be different.
  • the monohydrocarbylamine which can be utilized as the ⁇ - ⁇ -diimine neutral ligand can be, can comprise, or can consist essentially of, methyl amine, ethyl amine, propyl amine, butyl amine, or any combination thereof; alternatively, methyl amine; alternatively, ethyl amine; alternatively, propyl amine; or alternatively, butyl amine.
  • the dihydrocarbylamine which can be utilized as the ⁇ - ⁇ -diimine neutral ligand can be, can comprise, or can consist essentially of, dimethyl amine, diethyl amine, dipropyl amine, dibutylamine, or any combination thereof; alternatively, dimethyl amine; alternatively, diethyl amine; alternatively, dipropyl amine; or alternatively, dibutylamine.
  • the trihydrocarbylamine which can be utilized as the ⁇ - ⁇ -diimine neutral ligand can be, can comprise, or can consist essentially of, trimethyl amine, triethyl amine, tripropyl amine, tributyl amine, or any combination thereof; alternatively, trimethyl amine; alternatively, triethyl amine; alternatively, tripropyl amine; or alternatively, tributyl amine.
  • the organoaluminum compound which can be utilized in the processes described herein can comprise an aluminoxane, an alkylaluminum compound, or a combination thereof; alternatively, an aluminoxane; or alternatively, an alkylaluminum compound.
  • the alkylaluminum compound can be a trialkylaluminum, an alkylaluminum halide, an alkylaluminum alkoxide, or any combination thereof.
  • the alkylaluminum compound can be a trialkylaluminum, an alkylaluminum halide, or any combination thereof; alternatively, a trialkylaluminum, an alkylaluminum alkoxide, or any combination thereof; or alternatively, a trialkylaluminum.
  • the alkylaluminum compound can be a trialkylaluminum; alternatively, an alkylaluminum halide; or alternatively, an alkylaluminum alkoxide.
  • the organoaluminum compound (regardless of whether it is an aluminoxane, an alkylaluminum compound, or subspecies or individuals contained therein) can be substantially devoid of (or alternatively, devoid of) ⁇ , ⁇ -branched organyl groups (or alkyl group) and ⁇ , ⁇ -branched organyl groups (or alkyl groups).
  • substantially devoid of ⁇ , ⁇ -branched organyl groups (or alkyl group) and ⁇ , ⁇ - branched organyl groups (or alkyl group) can be taken to mean that less than 5, 4, 3, 2, 1 , 0.75, 0.5, 0.25, or 0.1 mole percent of the organoaluminum organyl groups are ⁇ , ⁇ -branched organyl groups (or alkyl groups) and ⁇ , ⁇ -branched organyl groups (or alkyl groups).
  • each alkyl group of any organoaluminum compound or any alkylaluminum compound disclosed herein independently can be a Ci to C 2 o alkyl group, a Ci to Cm alkyl group, or a Ci to C 6 alkyl group.
  • each alkyl group of any organoaluminum compound or any alkylaluminum compound disclosed herein independently can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group; alternatively, a methyl group, an ethyl group, a butyl group, a hexyl group, or an octyl group.
  • each alkyl group of any organoaluminum compound or any alkylaluminum compound disclosed herein independently can be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-butyl group, an n-hexyl group, or an n-octyl group; alternatively, a methyl group, an ethyl group, an n-butyl group, or an iso-butyl group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, an n-propyl group; alternatively, an n-butyl group; alternatively, an iso-butyl group; alternatively, an n-hexyl group; or alternatively, an n-octy
  • the organoaluminum compound (regardless of whether it is an aluminoxane, an alkylaluminum compound, or a subspecies or individuals contained therein) can be substantially devoid (or alternatively, devoid of) of ⁇ , ⁇ -branched alkyl groups and ⁇ , ⁇ -branched alkyl groups.
  • substantially devoid of ⁇ , ⁇ -branched alkyl groups and ⁇ , ⁇ -branched alkyl groups can be taken to mean that less than 5, 4, 3, 2, 1, 0.75, 0.5, 0.25, or 0.1 mole percent of the alkyl groups are ⁇ , ⁇ -branched alkyl groups and ⁇ , ⁇ -branched alkyl groups.
  • each halide of any alkylaluminum halide disclosed herein independently can be chloride, bromide, or iodide. In some aspects, each halide of any alkylaluminum halide disclosed herein can be chloride or bromide; or alternatively, chloride.
  • each alkoxide group of any alkylaluminum alkoxide disclosed herein independently can be a Q to C 2 o alkoxy group, a Ci to C 10 alkoxy group, or a Ci to C 6 alkoxy group.
  • each alkoxide group of any alkylaluminum alkoxide disclosed herein independently can be a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, or an octoxy group; alternatively, a methoxy group, an ethoxy group, a butoxy group, a hexoxy group, or an octoxy group.
  • each alkoxide group of any alkylaluminum alkoxide disclosed herein independently can be a methoxy group, an ethoxy group, an n-propoxy group, an n- butoxy group, an iso-butoxy group, an n-hexoxy group, or an n-octoxy group; alternatively, a methoxy group, an ethoxy group, an n-butoxy group, or an iso-butoxy group; alternatively, a methoxy group; alternatively, an ethoxy group; alternatively, an n-propoxy group; alternatively, an n-butoxy group; alternatively, an iso-butoxy group; alternatively, an n-hexoxy group; or alternatively, an n-octoxy group.
  • the trialkylaluminum compound can comprise, can consist essentially of, or can be, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, or mixtures thereof.
  • the trialkylaluminum compound can comprise, can consist essentially of, or can be, trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum, tri- n-octylaluminum, or mixtures thereof; alternatively, triethylaluminum, tri-n-butylaluminum, tri- isobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof; alternatively, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof.
  • the trialkylaluminum compound can comprise, can consist essentially of, or can be, trimethylaluminum; alternatively, triethylaluminum; alternatively, tripropylaluminum; alternatively, tri-n-butylaluminum; alternatively, tri-isobutylaluminum; alternatively, trihexylaluminum; or alternatively, tri-n-octylaluminum.
  • the alkylaluminum halide can comprise, can consist essentially of, or can be, diethylaluminum chloride, diethylaluminum bromide, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof.
  • the alkylaluminum halide can comprise, can consist essentially of, or can be diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof; or alternatively, diethylaluminum chloride; alternatively, diethylaluminum bromide; alternatively, ethylaluminum dichloride; or alternatively, ethylaluminum sesquichloride.
  • the aluminoxane can have a repeating unit characterized by the Formula I:
  • R' is a linear or branched alkyl group.
  • Alkyl groups for organoaluminum compounds are independently described herein and can be utilized without limitation to further describe the aluminoxanes having Formula I.
  • n of Formula I is greater than 1; or alternatively, greater than 2.
  • n can range from 2 to 15; or alternatively, from 3 to 10.
  • R' of the aluminoxane can be substantially devoid (or alternatively, devoid of) of ⁇ , ⁇ -branched alkyl groups and ⁇ , ⁇ -branched alkyl groups.
  • substantially devoid of ⁇ , ⁇ -branched alkyl groups and ⁇ , ⁇ - branched alkyl groups can be taken to mean that less than 5, 4, 3, 2, 1, 0.75, 0.5, 0.25, or 0.1 mole percent of the aluminoxane alkyl groups are ⁇ , ⁇ -branched alkyl groups and ⁇ , ⁇ -branched alkyl groups.
  • the aluminoxane can be a reaction product of water with an organoaluminum compound.
  • the organoaluminum compound can have the formula A1R A1 X H 3 .
  • X where x is an integer from 1 to 3 and each R can be any organyl group, hydrocarbyl group, or alkyl group (alternatively, any organyl group; alternatively, any hydrocarbyl groups; or alternatively, any alkyl group) of the organoaluminum compounds disclosed herein.
  • the organoaluminum having the formula A1R A1 X H 3 .
  • X of the aluminoxane which can be a reaction product of water with an organoaluminum compound having the formula A1R A1 X H 3 .
  • X is substantially devoid of (or alternatively, devoid of) ⁇ , ⁇ -branched and ⁇ , ⁇ -branched R A1 groups.
  • substantially devoid of ⁇ , ⁇ -branched and ⁇ , ⁇ -branched R A1 groups can be taken to mean that less than 5, 4, 3, 2, 1, 0.75, 0.5, 0.25, or 0.1 mole percent of the R A1 groups are ⁇ , ⁇ -branched and ⁇ , ⁇ - branched R A1 groups, organyl groups, hydrocarbyl groups, and/or alkyl group; alternatively, organyl groups; alternatively, hydrocarbyl groups; or alternatively, alkyl groups.
  • the aluminoxane can comprise, can consist essentially of, or can be, methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso- butylaluminoxane, t-butylaluminoxane, 1 -pentylaluminoxane, 2-pentylaluminoxane, 3- pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof.
  • MAO methylaluminoxane
  • MMAO modified methylaluminoxane
  • n-propylaluminoxane iso-propylaluminoxane
  • the aluminoxane can comprise, can consist essentially of, or can be, methylaluminoxane (MAO), a modified methylaluminoxane (MMAO), isobutylaluminoxane, t-butylaluminoxane, or mixtures thereof.
  • MAO methylaluminoxane
  • MMAO modified methylaluminoxane
  • isobutylaluminoxane t-butylaluminoxane, or mixtures thereof.
  • the aluminoxane can be, comprise, or consist essentially of, methylaluminoxane (MAO); alternatively, ethylaluminoxane; alternatively, modified methylaluminoxane (MMAO); alternatively, n-propylaluminoxane; alternatively, iso-propylaluminoxane; alternatively, n-butylaluminoxane; alternatively, sec-butylaluminoxane; alternatively, iso-butylaluminoxane; alternatively, t-butylaluminoxane; alternatively, 1-pentylaluminoxane; alternatively, 2- pentylaluminoxane; alternatively, 3-pentylaluminoxane; alternatively, iso-pentylaluminoxane; or alternatively, neopentylaluminoxane.
  • MAO methylaluminoxane
  • MMAO modified methylaluminoxane
  • the aluminoxane can be substantially devoid (or alternatively, devoid of) of ⁇ , ⁇ -branched alkyl groups and ⁇ , ⁇ -branched alkyl groups.
  • a aluminoxane substantially devoid of ⁇ , ⁇ -branched alkyl groups and ⁇ , ⁇ -branched alkyl groups can be taken to mean that less than 5, 4, 3, 2, 1, 0.75, 0.5, 0.25, or 0.1 mole percent of the aluminoxane alkyl groups are ⁇ , ⁇ -branched alkyl groups and ⁇ , ⁇ -branched alkyl groups.
  • the processes described herein can utilize an organic reaction medium.
  • the organic reaction medium can act as a solvent and/or a diluent in the processes described herein.
  • the organic reaction medium can comprise, can consist essentially of, or can be, a hydrocarbon, a halogenated hydrocarbon, or a combination thereof; alternatively, a hydrocarbon; or alternatively, a halogenated hydrocarbon(s).
  • hydrocarbons which can be utilized as the organic reaction medium can be an aliphatic hydrocarbon, an aromatic hydrocarbon, or any combination thereof; alternatively, an aliphatic hydrocarbon; or alternatively, an aromatic hydrocarbon.
  • the aliphatic hydrocarbon which can be utilized as the organic reaction medium can comprise, can consist essentially of, or can be, a saturated aliphatic hydrocarbon, an olefinic aliphatic hydrocarbon, or any combination thereof; alternatively, a saturated aliphatic hydrocarbon(s); or alternatively an olefinic aliphatic hydrocarbon(s).
  • halogenated hydrocarbons which can be utilized as the organic reaction medium can be a halogenated aliphatic hydrocarbon, a halogenated aromatic hydrocarbon, or any combination thereof; alternatively, a halogenated aliphatic hydrocarbon; or alternatively, a halogenated aromatic hydrocarbon.
  • the hydrocarbon, aliphatic hydrocarbon, saturated aliphatic hydrocarbon, or olefinic aliphatic hydrocarbon which can be utilized as the organic reaction medium can comprise, consist essentially of, or can be, a C 3 to C 18 , a C 4 to C 18 , or a C 5 to C 10 hydrocarbon(s), aliphatic hydrocarbon(s), saturated aliphatic hydrocarbon(s), or olefinic aliphatic hydrocarbon(s).
  • the aliphatic hydrocarbon(s) (saturated or olefinic) which can useful as an organic reaction medium can comprise, can consist essentially of, or can be, a C 8 to C 18 , a C 8 to C 16 , or alternatively, a C 10 to C 14 hydrocarbon(s), aliphatic hydrocarbon(s), saturated aliphatic hydrocarbon(s), or olefinic aliphatic hydrocarbon(s).
  • the hydrocarbon(s), aliphatic hydrocarbon(s), saturated aliphatic hydrocarbon(s), or olefinic hydrocarbon(s) can be cyclic or acyclic and/or can be linear or branched, unless otherwise specified.
  • Non-limiting examples of suitable hydrocarbon organic reaction mediums that can be utilized singly or in any combination include propane, butane(s), pentane(s), hexane(s), heptane(s), octane(s), decane(s), undecane(s), dodecane(s), tridecane(s), tetradecane(s), pentadecane(s), hexadecane(s), heptadecane(s), octadecane(s), hexene(s), heptene(s), octene(s), nonene(s), decene(s), dodecene(s), tetradecene(s), hexadecene(s), octadecene(s), or any combination thereof; alternatively, propane, butane(s), pentane(s), hexane(s), heptan
  • suitable acyclic aliphatic hydrocarbon organic reaction mediums can comprise, or can consist essentially of, propane, iso-butane, n-butane, butane (n-butane or a mixture of linear and branched C 4 acyclic aliphatic hydrocarbons), pentane (n-pentane or a mixture of linear and branched C 5 acyclic aliphatic hydrocarbons), hexane (n-hexane or mixture of linear and branched C 6 acyclic aliphatic hydrocarbons), heptane (n-heptane or mixture of linear and branched C 7 acyclic aliphatic hydrocarbons), octane (n-octane or a mixture of linear and branched C 8 acyclic aliphatic hydrocarbons), or any combination thereof.
  • a saturated aliphatic hydrocarbon can comprise, or consist essentially of 1 -octane, 1-decane, 1-dodecane, 1-tetradecane, 1 -hexadecane, 1-octadecane, or any combination thereof; alternatively, 1-decane, 1-dodecane, 1-tetradecane, or any combination thereof; alternatively, 1-decane; alternatively, 1-dodecane; or alternatively, 1-tetradecane.
  • an olefinic aliphatic hydrocarbon which can be utilized as the organic reaction medium can comprise, can consist essentially of, or can be, an alpha olefin(s); or alternatively, a normal alpha olefin(s).
  • the olefinic aliphatic hydrocarbon which can be utilized as the organic reaction medium can be, can comprise, or can consist essentially of, 1-octene, 1-decene, 1-dodecene, 1 -tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof; alternatively, 1 -decene, 1-dodecene, 1 -tetradecene, or any combination thereof; alternatively, 1-decene; alternatively, 1-dodecene; or alternatively, 1 -tetradecene.
  • the cyclic aliphatic hydrocarbon(s) which can be used as an organic reaction medium can comprise, or consist essentially of cyclohexane, methyl cyclohexane, or any combination thereof.
  • Non-limiting examples of suitable aromatic hydrocarbon(s) which can be used as an organic reaction medium can comprise, or can consist essentially of, a C 6 to C 10 aromatic hydrocarbon(s).
  • the aromatic hydrocarbon(s) which can be utilized as the organic reaction medium can comprise, or can consist essentially of benzene, toluene, xylene (including ortho-xylene, meta-xylene, para-xylene, or mixtures thereof), ethylbenzene, or combinations thereof.
  • Non-limiting examples of the halogenated aliphatic hydrocarbon(s) which can be used as the organic reaction medium can comprise, or can consist essentially of, a Ci to Ci 5 halogenated aliphatic hydrocarbon(s), a Ci to Cio halogenated aliphatic hydrocarbon(s), or a Ci to C 5 halogenated aliphatic hydrocarbon(s).
  • the halogenated aliphatic hydrocarbon(s) which can be utilized as an organic reaction medium can be cyclic or acyclic and/or can be linear or branched, unless otherwise specified.
  • the halogenated aliphatic hydrocarbon(s) which can be utilized as an organic reaction medium can comprise, or can consist essentially of methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, or combinations thereof.
  • Non-limiting examples of the halogenated aromatic hydrocarbon(s) which can be useful as the organic reaction medium can comprise, or can consist essentially of, a C 6 to C 2 o halogenated aromatic hydrocarbon(s), or a C 6 to C 10 halogenated aromatic hydrocarbon(s).
  • the halogenated aromatic hydrocarbon(s) which can be used as the organic reaction medium can comprise, or can consist essentially of, chlorobenzene, dichlorobenzene, or any combination thereof.
  • organic reaction medium can be made on the basis of convenience in processing.
  • isobutane can be chosen to be compatible with solvents and diluents used in processes using the product(s) of the processes described herein (e.g., using the product for the formation of polymer in a subsequent processing step).
  • the organic reaction medium can be chosen to be easily separable from the one or more oligomers in the oligomer product.
  • an oligomer of the oligomer product can be utilized as the reaction system solvent.
  • the oligomer product can be formed in a reaction zone.
  • the reaction zone of any process described herein can comprise a continuous stirred tank reactor, a plug flow reactor, or any combination thereof; alternatively, a continuous stirred tank reactor; or alternatively, a plug flow reactor.
  • the reaction zone of any process described herein can comprise a continuous stirred tank reactor, a loop reactor, a solution reactor, a tubular reactor, a recycle reactor, a bubble reactor, or any combination thereof; alternatively, a continuous stirred tank reactor; alternatively, a loop reactor; alternatively, a solution reactor; alternatively, a tubular reactor; alternatively, a recycle reactor; or alternatively, a bubble reactor.
  • the reaction zone in which the oligomer product can be formed can comprise multiple reactors; or alternatively, only one reactor.
  • each of the reactors can be the same or can be different types of reactors.
  • each reactor independently can be any reactor described herein, and the reactors can be arranged in series, parallel, or any combination thereof; alternatively, in series; or alternatively, in parallel.
  • each reactor can be operated independent of each other (regardless of whether they are operated in series or parallel). As such, the contact modes (if needed), the conditions under which the oligomer product can be formed, the oligomer product formation parameters under which the oligomer product can be formed, and/or the reaction zone conditions can be different for each reactor. In particular, when the reaction zone comprises multiple reactors in series, each reactor can be operated to achieve different goals.
  • a first reactor can be operated to i) contact ethylene, the metal salt and the heteroatomic ligand (or alternatively, ethylene, the first metal salt, and the heteroatomic ligand complexed to the first metal salt), the optional organic reaction medium and the optional hydrogen and ii) initiate production of the oligomer product under a first set of conditions capable of producing the oligomer product to some intermediate ethylene conversion and the effluent of the first reactor transferred to a second reactor operated to achieve the desired ethylene conversion under a second set of conditions capable of producing the oligomer product with or without additional ethylene, the metal salt, the heteroatomic ligand (or alternatively, ethylene, the first metal salt, and the heteroatomic ligand complexed to the first metal salt), the optional organic reaction medium and the optional hydrogen being added to the reactor/reaction zone.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, conditions that can comprise, either singly or in any combination, a heteroatomic ligand molar equivalent concentration, a heteroatomic ligand first metal salt complex molar equivalent concentration, an equivalent molar ratio of second metal salt to heteroatomic ligand of the heteroatomic ligand metal salt complex, an equivalent molar ratio of second metal salt to heteroatomic ligand metal salt complex, an equivalent molar ratio of metal salt to heteroatomic ligand, an aluminum of the organoaluminum compound to heteroatomic ligand molar equivalent ratio, an aluminum of the organoaluminum compound to heteroatomic ligand first metal salt complex molar equivalent ratio, an aluminum of the organoaluminum compound concentration, an ethylene partial pressure, an ethylene to organic reaction medium mass ratio, a temperature (or an average temperature), an Schulz-Flory K value, a hydrogen partial pressure, and/or a hydrogen to ethylene
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, conditions that can comprise, a heteroatomic ligand molar equivalent concentration; alternatively, a heteroatomic ligand first metal salt complex molar equivalent concentration; alternatively, an equivalent molar ratio of second metal salt to heteroatomic ligand of the heteroatomic ligand metal salt complex; alternatively, an equivalent molar ratio of second metal salt to heteroatomic ligand metal salt complex; alternatively, an equivalent molar ratio of metal salt to heteroatomic ligand; alternatively, an aluminum of the organoaluminum compound to heteroatomic ligand molar equivalent ratio; alternatively, an aluminum of the organoaluminum compound to heteroatomic ligand first metal salt complex molar equivalent ratio; alternatively, an aluminum of the organoaluminum compound concentration; alternatively, an ethylene partial pressure; alternatively, an ethylene to organic reaction medium mass ratio; alternatively, a temperature (or an average temperature); alternatively, an Schulz
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a particular heteroatomic ligand molar equivalent concentration (or alternatively, heteroatomic ligand metal salt complex molar equivalent concentration).
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a minimum heteroatomic ligand molar equivalent concentration (or alternatively, heteroatomic ligand metal salt complex molar equivalent concentration) of 1 x 10 "6 , 1 x 10 "5 , or 1 x 10 "4 heteroatomic ligand molar equivalents/kg (or alternatively, heteroatomic ligand metal salt complex molar equivalents/kg) based upon the kg mass of the reaction solution; alternatively or additionally, at a maximum heteroatomic ligand molar equivalent concentration (or alternatively, heteroatomic ligand metal salt complex molar equivalent concentration) of 1 x 10 "1 , 1 x 10 "2 , or 1 x 10 "3 heteroatomic ligand molar equivalents/kg (or alternatively, heteroatomic ligand metal salt complex molar equivalents/kg) based upon the kg mass of the reaction solution.
  • a minimum heteroatomic ligand molar equivalent concentration or alternatively, heteroatomic lig
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a heteroatomic ligand molar equivalent concentration (or alternatively, heteroatomic ligand metal salt complex molar equivalent concentration) in the range of any minimum heteroatomic ligand molar equivalent concentration (or alternatively, heteroatomic ligand metal salt complex molar equivalent concentration) disclosed herein to any maximum heteroatomic ligand molar equivalent concentration (or alternatively, heteroatomic ligand metal salt complex molar equivalent concentration) disclosed herein.
  • a heteroatomic ligand molar equivalent concentration or alternatively, heteroatomic ligand metal salt complex molar equivalent concentration in the range of any minimum heteroatomic ligand molar equivalent concentration (or alternatively, heteroatomic ligand metal salt complex molar equivalent concentration) disclosed herein to any maximum heteroatomic ligand molar equivalent concentration (or alternatively, heteroatomic ligand metal salt complex molar equivalent concentration) disclosed herein.
  • the oligomer product can be formed, the reaction zone can have, or the reaction zone can operate, at an heteroatomic ligand molar equivalent concentration (or alternatively, heteroatomic ligand metal salt complex molar equivalent concentration) in the range of 1 x 10 "6 to 1 x 10 "1 , 1 x 10 "5 to 1 x 10 "2 , or 1 x 10 "4 to 1 x 10 "3 heteroatomic ligand molar equivalents/kg (or alternatively, heteroatomic ligand metal salt complex molar equivalents/kg) based upon the kg mass of the reaction solution.
  • Other heteroatomic ligand molar equivalent concentration (or alternatively, heteroatomic ligand metal salt complex molar equivalent concentration) ranges that can be utilized are readily apparent to those skilled in the art with the aid of this disclosure.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a particular equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex (or a particular equivalent molar ratio of the second metal salt to the heteroatomic ligand first metal salt complex).
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a minimum equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand first metal salt complex (or a minimum equivalent molar ratio of the second metal salt to the heteroatomic ligand first metal salt complex) of 0.1 : 1, 0.25: 1, 0.5: 1, 1.2: 1, 2: 1, or 3 : 1 ; alternatively or additionally, a maximum equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand first metal salt complex (or a maximum equivalent molar ratio of the second metal salt to the heteroatomic ligand first metal salt complex) of 100: 1, 50: 1, 25: 1, 17: 1 or 10: 1.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, an equivalent molar ratio of the second metal salt to heteroatomic ligand of the heteroatomic ligand first metal salt complex (or an equivalent molar ratio of the second metal salt to the heteroatomic ligand first metal salt complex) in the range of any minimum equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand first metal salt complex (or a minimum equivalent molar ratio of the second metal salt to the heteroatomic ligand first metal salt complex) disclosed herein to any maximum equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand first metal salt complex (or maximum equivalent molar ratio of the second metal salt to the heteroatomic ligand first metal salt complex)disclosed herein.
  • the equivalent molar ratio of the second metal salt to heteroatomic ligand of the heteroatomic ligand first salt complex can be in the range of from 0.1 : 1 to 100: 1, from 0.25: 1 to 50: 1, from 0.5: 1 to 50: 1, from 1.2: 1 to 50: 1, from 1.2: 1 to 25: 1 ; from 2: 1 to 17: 1, or from 3 : 1 to 10: 1.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a particular equivalent molar ratio of the metal salt to heteroatomic ligand.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a minimum equivalent molar ratio of the metal salt to heteroatomic ligand of 1.25: 1, 1.5: 1, 2: 1, 2.5: 1 or 3: 1 ; alternatively or additionally, a maximum equivalent molar ratio of iron salt to heteroatomic ligand of 100: 1, 75: 1 50: 1, 40: 1, 30: 1, 25: 1, 20: 1, 15: 1, or 10: 1.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, an equivalent molar ratio of the metal salt to heteroatomic ligand in the range of any minimum equivalent molar ratio of the metal salt to heteroatomic ligand disclosed herein to any maximum equivalent molar ratio of the metal salt to heteroatomic ligand disclosed herein.
  • the equivalent molar ratio of the metal salt to heteroatomic ligand can be in the range of from 1.25 to 100: 1, from 1.5 to 75: 1, from 1.5 to 50: 1, from 1.5: 1 to 40: 1 ; from 2: 1 to 40: 1, from 2.5: 1 to 40: 1, from 3 : 1 to 30: 1, from 3 : 1 to 25: 1, from 3 : 1 to 20: 1, from 3 : 1 to 15: 1, or from 3 : 1 to 10: 1.
  • Other ranges of the equivalent molar ratio of the metal salt to heteroatomic ligand that can be utilized will be readily apparent to those skilled in the art with the aid of this disclosure.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at a particular aluminum of the organoaluminum compound to heteroatomic ligand molar equivalent ratio (or alternatively, aluminum of the organoaluminum compound to heteroatomic ligand first metal salt complex molar equivalent ratio).
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a minimum aluminum of the organoaluminum compound to heteroatomic ligand molar equivalent ratio (or alternatively, aluminum of the organoaluminum compound to heteroatomic ligand first metal salt complex molar equivalent ratio), of 100: 1, 200: 1, 300: 1, or 400: 1 ; alternatively or additionally, a maximum aluminum of the organoaluminum compound to heteroatomic ligand molar equivalent ratio (or alternatively, aluminum of the organoaluminum compound to heteroatomic ligand first metal salt complex molar equivalent ratio), of 5,000: 1, 2,000: 1, 1,500: 1, or 1,000: 1.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, an aluminum of the organoaluminum compound to heteroatomic ligand molar equivalent ratio (or alternatively, aluminum of the organoaluminum compound to heteroatomic ligand first metal salt complex molar equivalent ratio), in the range of any minimum aluminum of the organoaluminum compound to heteroatomic ligand molar equivalent ratio (or alternatively, aluminum of the organoaluminum compound to heteroatomic ligand first metal salt complex molar equivalent ratio), disclosed herein to any maximum aluminum of the organoaluminum compound to heteroatomic ligand molar equivalent ratio (or alternatively, aluminum of the organoaluminum compound to heteroatomic ligand first metal salt complex molar equivalent ratio), disclosed herein.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, an aluminum of the organoaluminum compound to heteroatomic ligand molar equivalent ratio (or alternatively, aluminum of the organoaluminum compound to heteroatomic ligand first metal salt complex molar equivalent ratio), in the range of 100: 1 to 5,000: 1, 200: 1 to 2,000: 1, 300: 1 to 1,500: 1, or 400: 1 to 1,000: 1.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a particular aluminum of the organoaluminum compound concentration, also referred to as aluminum concentration or Al concentration.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a minimum Al concentration of 0.3 mmol Al/kg, 0.75 mmol Al/kg, 0.9 mmol Al/kg, or 1.1 mmol Al/kg based upon the kg mass of the reaction solution; alternatively or additionally, a maximum Al concentration of 15 mmol Al/kg, 12.5 mmol Al/kg, 10 mmol Al/kg, 7.5 mmol Al/kg, 5 mmol Al/kg, 2.6 mmol Al/kg, 2.2 mmol Al/kg, 1.8 mmol Al/kg, or 1.5 mmol Al/kg based upon the kg mass of the reaction solution.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, an Al concentration in the range of any minimum Al concentration disclosed herein to any maximum Al concentration disclosed herein.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, an Al concentration in the range of 0.3 mmol Al/kg to 15 mmol Al/kg, 0.3 mmol Al/kg to 10 mmol Al/kg, 0.5 mmol Al/kg to 10 mmol Al/kg, 0.5 mmol Al/kg to 7.5 mmol Al/kg, 0.5 mmol Al/kg to 5 mmol Al/kg, 0.75 mmol Al/kg to 2.6 mmol Al/kg, 0.75 mmol Al/kg to 2.2 mmol Al/kg, 0.9 mmol Al/kg to 1.8 mmol Al/kg, 1.1 mmol Al/kg to 1.8 mmol Al/kg, or 1.1 mmol Al/kg,
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a minimum ethylene partial pressure of 50 psi (344 KPa), 100 psi (689 KPa), 250 psi (1.72 MPa), 500 psi (3.45 MPa), or 800 psi (5.52 MPa); alternatively or additionally, a maximum ethylene partial pressure of 5,000 psi (34.5 MPa), 3,000 psi (20.9 MPa), 2,000 psi (13.8 MPa), 1,500 psi (10.3 MPa), or 1000 psi (6.89 MPa).
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, an ethylene partial pressure in the range of any minimum ethylene partial pressure disclosed herein to any maximum ethylene partial pressure disclosed herein.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, an ethylene partial pressure in the range of 50 psi (344 KPa) to 5,000 psi (34.5 MPa), 100 psi (689 KPa) to 3,000 psi (20.9 MPa), 250 psi (1.72 MPa) to 2,000 psi (13.8 MPa), 500 psi (3.45 MPa) to 2,000 psi (13.8 MPa), 500 psi (3.45 MPa) to 1,500 psi (10.3 MPa), or 800 psi (5.52 kPa) to 1000 psi (6.89 MPa).
  • Other ethylene partial pressure ranges are readily apparent to those skilled in
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a minimum ethylene: organic reaction medium mass ratio of 0.8: 1, 1 : 1, 1.25: 1, or 1.5: 1; alternatively, or additionally, a maximum ethylene: organic reaction medium mass ratio of 4.5: 1, 4: 1, 3.5: 1, 3 : 1, or 2.5: 1.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, an ethylene: organic reaction medium mass ratio in the range of any minimum ethylene: organic reaction medium mass ratio disclosed herein to any maximum ethylene: organic reaction medium mass ratio disclosed herein.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, an ethylene: organic reaction medium mass ratio in the range of 0.8: 1 to 4.5 : 1 , 1 : 1 to 4: 1 , 1 : 1 to 3.5 : 1 , 1.25 : 1 to 3 : 1 , or 1.5 : 1 to 2.5 : 1.
  • ethylene: organic reaction medium mass ratio ranges that can be utilized are readily apparent to those skilled in the art with the aid of this disclosure.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a minimum reaction zone temperature of 0 °C, 25 °C, 40 °C, 50 °C, or 60 °C; alternatively or additionally, a maximum reaction zone reaction zone temperature of 200 °C, 150 °C, 125 °C, 1 10 °C, or 100 °C.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a reaction zone temperature in the range of any minimum temperature disclosed herein to any maximum temperature disclosed herein.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a reaction zone temperature in the range of 0 °C to 200 °C, 25 °C to 150 °C, 40 °C to 125 °C, 50 °C to 125 °C, 50 °C to 1 10 °C, or 60 °C to 100 °C.
  • a reaction zone temperature in the range of 0 °C to 200 °C, 25 °C to 150 °C, 40 °C to 125 °C, 50 °C to 125 °C, 50 °C to 1 10 °C, or 60 °C to 100 °C.
  • Other temperature ranges that can be utilized are readily apparent to those skilled in the art with the aid of this disclosure.
  • the temperatures provided herein accordingly can be average minimum reaction zone temperatures, average maximum reaction zone temperatures, or average reaction zone temperature.
  • the oligomer product can have a minimum Schulz- Flory K value of 0.4, 0.45, 0.5 or, 0.55; alternatively or additionally, a maximum Schulz-Flory K value of 0.9, 0.85, 0.8, 0.75, 0.7 or, 0.65.
  • the oligomer product can have a Schulz-Flory K value in the range of any minimum Schulz-Flory K value disclosed herein to any maximum Schulz-Flory K value disclosed herein.
  • the oligomer product can have a Schulz-Flory K value in the range from 0.4 to 0.9; alternatively, from 0.4 to 0.8; alternatively, from 0.5 to 0.8; alternatively, from 0.5 to 0.7; alternatively, from 0.55 to 0.7.
  • Other oligomer product Schulz-Flory K value ranges are readily apparent to those of ordinary skill in the art from the present disclosure.
  • the Schulz-Flory K value can be determined using any one or more of the C 8 , C 10 , C 12 , C 14 , or C 16 oligomer product.
  • the Schulz-Flory K value can be an average of any two or more Schulz-Flory K values using different adjacent pairs of produced oligomers described herein.
  • the Schulz-Flory K value can be an average of any two Schulz-Flory K values described herein; alternatively, any three Schulz-Flory K values described herein; or alternatively, any four Schulz-Flory K values described herein.
  • the Schulz-Flory K value can be determined using the C 8 and Cm oligomer product; alternatively, the Cm and Cn oligomer product; alternatively, the Cn and C u oligomer product; alternatively, the C u and Ci 6 oligomer product; alternatively, the C 8 , Ci 0 , and Cn oligomer product, or alternatively, the Ci 0 , Cn, and C u oligomer product, among other combinations of oligomer product.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a minimum hydrogen partial pressure of 1 psi (6.9 kPa), 2 psi ( 14 kPa); 5 psi (34 kPa), 10 psi (69 kPa), 15 psi (103 kPa), 20 psi (138 kPa), 30 psi (206 kPa); alternatively or additionally, a maximum hydrogen partial pressure of 150 psi ( 1.03 MPa), 100 psi (689 kPa), 75 psi (517 kPa), or 50 psi (345 kPa).
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a hydrogen partial pressure in the range of any minimum hydrogen partial pressure disclosed herein to any maximum hydrogen partial pressure disclosed herein.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a hydrogen partial pressure in the range of 1 psi (6.9 kPa) to 150 psi (1.4 MPa), from 5 psi (34 kPa) to 100 psi (689 kPa), from 10 psi (69 kPa) to 100 psi (689 kPa), or from 15 psi ( 100 kPa) to 75 psi (517 kPa).
  • Other hydrogen partial pressure ranges that can be utilized are readily apparent to those of ordinary skill in the art with the aid of this disclosure.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a minimum hydrogen to ethylene mass ratio of (0.05 g hydrogen)/(kg ethylene), (0.1 g hydrogen)/(kg ethylene), (0.25 g hydrogen)/(kg ethylene), (0.4 g hydrogen)/(kg ethylene), or (0.5 g hydrogen)/(kg ethylene); alternatively or additionally, a maximum hydrogen to ethylene mass ratio can be (5 g hydrogen)/(kg ethylene), (3 g hydrogen)/(kg ethylene), (2.5 g hydrogen)/(kg ethylene), (2 g hydrogen)/(kg ethylene), or ( 1.5 g hydrogen)/(kg ethylene).
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a hydrogen to ethylene mass ratio in the range of any minimum hydrogen to ethylene mass ratio disclosed herein to any maximum hydrogen to ethylene mass ratio disclosed herein.
  • the oligomer product can be formed at, the reaction zone can have, or the reaction zone can operate at, a hydrogen to ethylene mass ratio in the range of (0.05 g hydrogen)/(kg ethylene) to (5 g hydrogen)/(kg ethylene), from (0.25 g hydrogen)/(kg ethylene) to (5 g hydrogen)/(kg ethylene), from (0.25 g hydrogen)/(kg ethylene) to (4 g hydrogen)/(kg ethylene), from (0.4 g hydrogen)/(kg ethylene) to (3 g hydrogen)/(kg ethylene), from (0.4 g hydrogen)/(kg ethylene) to (2.5 g hydrogen)/(kg ethylene), from (0.4 g hydrogen)/(kg ethylene) to (2 g hydrogen)/(kg ethylene), or from (0.5 g hydrogen)/(kg ethylene) to (2 g hydrogen)/(kg ethylene).
  • Other hydrogen to ethylene mass ratio ranges that can be utilized are readily apparent to those of ordinary skill in the art with the aid of this disclosure.
  • the presence of the second metal salt in processes utilizing a heteroatomic ligand first metal salt complex can increase the stability of and/or can increase the lifetime of the active catalytic species produced by contacting the heteroatomic ligand first metal salt with the organoaluminum compound.
  • processes utilizing any second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex can have a C 4 -C 2 o productivity at least 5%, 10 % 13 %, 15 %, or 17 % greater than the C 4 -C 2 o productivity of an otherwise similar process wherein an equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex (or second metal salt to the heteroatomic ligand metal salt complex) is less than 0.1 : 1.
  • the C 4 -C 2 o productivity for processes utilizing a second metal salt and a heteroatomic ligand first metal salt complex can be less than or equal to 100 %, 75%, 50 %, or 40 % the C -C 20 productivity of an otherwise similar process wherein an equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex (or second metal salt to the heteroatomic ligand metal salt complex) is less than 0.1 : 1.
  • the C -C 20 productivity increase can range from any minimum C -C 20 productivity increase disclosed herein to any maximum C -C 20 productivity increase disclosed herein.
  • the C -C 20 productivity can be in the range of 5 % to 100 %, 10 % to 100 %, 10 % to 75 %, 13 % to 50 %, 13 % to 50%, 15 % to 40 %, or 17 % to 40 % greater than the C -C 20 productivity of an otherwise similar process wherein an equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex (or second metal salt to the heteroatomic ligand metal salt complex) is less than 0.1 : 1.
  • Other C 4 - C 20 productivity increase ranges are readily apparent to those skilled in the art with the aid of this disclosure.
  • Equivalent molar ratios of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex (or second metal salt to the heteroatomic ligand metal salt complex) for the processes described herein are independently described herein and these independently described equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex (or second metal salt to the heteroatomic ligand metal salt complex) can be utilized without limitation to further describe the C 4 -C 20 productivity increases when compared to an otherwise similar process wherein an equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex (or second metal salt to the heteroatomic ligand metal salt complex) is less than 0.1 : 1.
  • an equivalent molar ratio of metal salt to heteroatomic greater than the 1 : 1 ratio to produce the heteroatomic ligand metal salt complex can increase the stability of and/or can increase the lifetime of the active catalytic species produced by contacting the metal salt, heteroatomic ligand, and organoaluminum compound.
  • processes utilizing a equivalent molar ratio of metal salt to heteroatomic ligand greater than the 1 : 1 equivalent molar ratio needed to produce the heteroatomic ligand metal salt complex can have a C 4 -C 2 o productivity at least 100 %, 200 % 300 %, 400 %, or 500 % greater than the C 4 -C 2 o productivity of an otherwise similar process wherein an equivalent molar ratio of the metal salt to the heteroatomic ligand is less than 1.1 : 1.
  • the C 4 -C 2 o productivity for processes utilizing a metal salt and a heteroatomic ligand can be less than or equal to 10,000 %, 5,000 %, 3,000 %, or 1 ,000 % the C 4 -C 2 o productivity of an otherwise similar process wherein an equivalent molar ratio of the metal salt to the heteroatomic ligand is less than 1.1 : 1.
  • the C 4 -C 20 productivity increase can range from any minimum C 4 -C 20 productivity increase disclosed herein to any maximum C -C 20 productivity increase disclosed herein.
  • the C 4 -C 20 productivity can be in the range of 100 % to 10,000 %, 200 % to 5,000 %, 300 % to 3,000 %, 400 % to 3,000 %, 500 % to 3,000%, 300 % to 1 ,000 %, 400 % to 1 ,000 %, or 500 % to 1,000 % of the C -C 20 productivity of an otherwise similar process wherein an equivalent molar ratio of the metal salt to the heteroatomic ligand is less than 1.1 : 1.
  • Other C -C 20 productivity increase ranges are readily apparent to those skilled in the art with the aid of this disclosure.
  • Equivalent molar ratios of metal salt to heteroatomic ligand for the processes described herein are independently described herein and these independently described equivalent molar ratio of metal salt to heteroatomic ligand can be utilized without limitation to further describe the C -C 20 productivity increases when compared to an otherwise similar process wherein an equivalent molar ratio of the metal salt to the heteroatomic ligand is less than 1.1 : 1.
  • the processes described herein can produce an oligomer product with high selectivity to linear alpha olefins; or alternatively, to normal alpha olefins.
  • the processes described herein can produce a reactor effluent wherein the C 6 olefin oligomer product has a 1 -hexene content of at least 98.5 wt. %; alternatively, at least 98.75 wt. %; alternatively, at least 99.0 wt. %; or alternatively, at least 99.25 wt. %.
  • the processes described herein can produce a reactor effluent wherein the C 8 olefin oligomer product has a 1 -octene content of at least 98 wt. %; alternatively, at least 98.25 wt. %; alternatively, at least 98.5 wt. %; alternatively, at least 98.75 wt. %; or alternatively, at least 99.0 wt. %.
  • the processes described herein can produce a reactor effluent wherein the Ci 0 olefin oligomer product has a 1 -decene content of at least 97.5 wt. %; alternatively, at least 97.75 wt.
  • the processes described herein can produce a reactor effluent wherein the C n olefin oligomer product has a 1 -dodecene content of at least 96.5 wt. %; alternatively, at least 97 wt. %; alternatively, at least 97.5 wt. %; alternatively, at least 97.75 wt. %; or alternatively, at least 98.0 wt. %.
  • the processes described herein can produce a reactor effluent wherein the oligomer product can comprise any combination of any C 6 olefin oligomer product 1 -hexene content described herein, any C 8 olefin oligomer product 1 -octene content described herein, any C 10 olefin oligomer product 1 -decene content described herein, and/or any C 12 olefin oligomer product 1 -dodecne content described herein.
  • the processes described herein can produce a reactor effluent having a C 6 olefin oligomer product 1 -hexene content of at least 99 wt.
  • each substituent of any aspect and/or embodiment calling for a substituent can be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen; alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxy group.
  • each hydrocarbyl group or substituent of any aspect and/or embodiment calling for a substituent can be a C ⁇ to Cjo, or a C ⁇ to C5 hydrocarbyl group.
  • each hydrocarboxy group or substituent of any aspect and/or embodiment calling for a substituent can be a C ⁇ to Cjo, or a C ⁇ to C5 hydrocarboxy group.
  • any halide substituent of any aspect and/or embodiment calling for a halide substituent can be a fluoride, chloride, bromide, or iodide; alternatively, a fluoride or chloride.
  • any halide substituent of any aspect and/or embodiment calling for a substituent can be a fluoride; alternatively, a chloride; alternatively, a bromide; or alternatively, an iodide.
  • any hydrocarbyl group or substituent of any aspect and/or embodiment calling for a substituent can be an alkyl group, an aryl group, or an aralkyl group; alternatively, an alkyl group; alternatively, an aryl group; or alternatively, an aralkyl group.
  • any alkyl group of any aspect and/or embodiment calling for a substituent can be a methyl group, an ethyl group, an n- propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methyl- 1 -butyl group, a tert-pentyl group, a 3 -methyl- 1 -butyl group, a 3-methyl-2-butyl group, or a neo-pentyl group; alternatively, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a neo-pentyl group; alternatively, a methyl group; alternatively, an ethyl group; an iso
  • any aryl group of any aspect and/or embodiment calling for a substituent can be phenyl group, a tolyl group, a xylyl group, or a 2,4,6- trimethylphenyl group; alternatively, a phenyl group; alternatively, a tolyl group, alternatively, a xylyl group; or alternatively, a 2,4,6-trimethylphenyl group.
  • any aralkyl group of any aspect and/or aspect calling for a substituent can be benzyl group or an ethylphenyl group (2-phenyleth- 1 -yl or 1-phenyleth-l -yl); alternatively, a benzyl group; alternatively, an ethylphenyl group; alternatively, a 2- phenyleth-l-yl group; or alternatively, a 1-phenyleth-l-yl group.
  • any hydrocarboxy group or substituent of any aspect and/or embodiment calling for a substituent can be an alkoxy group, an aryloxy group, or an aralkoxy group; alternatively, an alkoxy group; alternatively, an aryloxy group; or alternatively, an aralkoxy group.
  • any alkoxy group of any aspect and/or embodiment calling for a substituent can be a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a 2- methyl-l-butoxy group, a tert-pentoxy group, a 3 -methyl- 1-butoxy group, a 3-methyl-2-butoxy group, or a neo-pentoxy group; alternatively, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, or a neo-pentoxy group; alternatively, a methoxy group; alternatively, an ethoxy group; alternatively, an isopropoxy group; alternatively, a tert-butoxy group
  • any aryloxy group of any aspect and/or embodiment calling for a substituent can be phenoxy group, a toloxy group, a xyloxy group, or a 2,4,6-trimethylphenoxy group; alternatively, a phenoxy group; alternatively, a toloxy group, alternatively, a xyloxy group; or alternatively, a 2,4,6- trimethylphenoxy group.
  • any aralkoxy group of any aspect or aspect calling for a substituent can be a benzoxy group.
  • Embodiment 1 A process for forming an oligomer product comprising: a) introducing into a reaction zone i. ethylene; ii. a heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt where the first metal salt is an iron salt, a cobalt salt, or a combination thereof; iii.
  • an equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex is at least 0.5: 1 (or any other equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex, or second metal salt to the heteroatomic ligand metal salt complex, disclosed herein) and where the second metal salt is an iron salt, a cobalt salt, or any combination thereof; iv. an organoaluminum compound; v. optionally hydrogen; and vi. optionally an organic reaction medium; and b) forming an oligomer product in the reaction zone.
  • an equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex is at least 0.5: 1 (or any other equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex, or second metal salt to the heteroatomic ligand metal salt complex, disclosed herein) and where the second metal salt is an iron salt
  • Embodiment 3 The process of embodiment 1 or 2, wherein a C 4 -C 2 o productivity is at least 10 % greater than the C 4 -C 2 o productivity of an otherwise similar process wherein an equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex (or second metal salt to the heteroatomic ligand metal salt complex) is less than 0.1 : 1.
  • Embodiment 4 The process of any one of embodiments 1 to 3, where the first metal salt comprises an iron halide, an iron ⁇ -diketonate, an iron carboxylate, or any combination thereof and the second metal salt comprises an iron halide, an iron ⁇ -diketonate, an iron carboxylate, or any combination thereof.
  • Embodiment 5 The process of any one of embodiments 1 to 4, where the first metal salt and the second metal salt are the same or different.
  • Embodiment 6 A process for forming an oligomer product comprising: a) introducing into a reaction zone i. ethylene; ii. a heteroatomic ligand; iii. a metal salt where 1) the metal salt is an iron salt, a cobalt salt, or any combination thereof, and 2) an equivalent molar ratio of the metal salt to the heteroatomic ligand is at least 1.5: 1 (or any other equivalent molar ratio of the metal salt to the heteroatomic ligand disclosed herein); iv. an organoaluminum compound; v. optionally hydrogen; and vi. optionally an organic reaction medium; and b) forming an oligomer product in the reaction zone.
  • Embodiment 7 The process of embodiment 6, wherein the equivalent molar ratio of the metal salt to the heteroatomic ligand ranges from 1.5: 1 to 50: 1 (or any other equivalent molar ratio of the metal salt to the heteroatomic ligand disclosed herein).
  • Embodiment 8 The process of embodiment 6 or 7, wherein a C 4 -C 2 o productivity is at least 100 % greater than the C 4 -C 2 o productivity of an otherwise same process wherein an equivalent molar ratio of the metal salt to the heteroatomic ligand is less than 1.1 : 1.
  • Embodiment 9 The process of any one of embodiments 6 to 8, where the metal salt comprises an iron halide, an iron ⁇ -diketonate, an iron carboxylate, or any combination thereof.
  • Embodiment 10 The process of any one of embodiments 1 to 9, wherein the heteroatomic ligand or the heteroatomic ligand of the heteroatomic ligand metal salt complex comprises 1 ) a bidentate metal salt complexing moiety, or 2) a tridentate metal salt complexing moiety, wherein the bidentate metal salt complexing moiety and the tridentate metal salt complexing moiety each independently comprise at least two metal salt complexing groups selected from the group consisting of an imine group and an aromatic nitrogen atom containing group.
  • Embodiment 1 1. The process of any one of embodiments 1 to 10, wherein the heteroatomic ligand or the heteroatomic ligand of the metal salt complex comprises an a-diimine, a pyridine bisimine, a phenanthroline imine, or any combination thereof.
  • Embodiment 12 The process of embodiment 1 1, wherein the heteroatomic ligand or the heteroatomic ligand of the metal salt complex is the ⁇ -diimine and the ⁇ -diimine comprises i) an a- diimine group, ii) a first imine group consisting of a hydrocarbyl group or substituted hydrocarbyl group attached to a first imine nitrogen atom of the ⁇ -diimine group, and iii) a second imine group comprising a first metal salt complexing group and a linking group linking the first metal salt complexing group to a second imine nitrogen atom of the ⁇ -diimine group.
  • Embodiment 13 The process of embodiment 1 1, wherein the a-diimine comprises i) an a- diimine group derived from an aromatic diacyl compound, ii) a first imine group consisting of an aryl group or substituted aryl group, and iii) a second imine group comprising a diarylphosphinyl first metal salt complexing group and a -CH 2 CH 2 - linking group linking the diarylphosphinyl first metal salt complexing group to the second imine nitrogen atom.
  • Embodiment 14 The process of embodiment 1 1, wherein the ⁇ -diimine comprises i) an a- diimine group derived from acenaphthenequinone, phenanthrenequinone, or pyrenequinone, ii) a first imine group consisting of an 2,6-dihydrocarbylphenyl group, and iii) a second imine group comprising a diphenylphosphinyl first metal salt complexing group or a di(substituted phenyl)phosphinyl first metal complexing group and a -CH 2 CH 2 - linking group linking the first metal salt complexing group to the second imine nitrogen atom.
  • the ⁇ -diimine comprises i) an a- diimine group derived from acenaphthenequinone, phenanthrenequinone, or pyrenequinone, ii) a first imine group consisting of an 2,6
  • Embodiment 15 The process of any one of embodiments 1 to 14 wherein the heteroatomic ligand metal salt complex has a structure selected from the group consisting of ADIFe I, ADIFe II, ADIFe III, ADIFe IV, ADIFe V, ADIFe VI, ADIFe VII, ADIFe VIII, ADIFe IX, ADIFe X, ADIFe XI, ADIFe XII, ADIFe XIII, and ADIFe XIV.
  • Embodiment 16 The process of embodiment 1 1, wherein the heteroatomic ligand or the heteroatomic ligand of the heteroatomic ligand metal salt complex is the pyridine bisimine and the pyridine bisimine comprises i) a 2,6-bis[(arylimine)hydrocarbyl]pyridine wherein the aryl groups can be the same or different, ii) a bis [(substituted arylimine)hydrocarbyl]pyridine wherein the substituted aryl groups can be the same or different, or iii) an [(arylimine)hydrocarbyl], [(substituted arylimine)hydrocarbyl]pyridine, or iii) an [(arylimine)hydrocarbyl], [(substituted arylimine)hydrocarbyl]- pyridine.
  • Embodiment 17 The process of embodiment 16, wherein the pyridine bisimine has 1) one, two, or three of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group, or a secondary carbon atom group and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 2) one of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen is a tertiary carbon atom group, none, one, or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group or a secondary carbon atom group, and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 3) two
  • Embodiment 18 The process of embodiment 16, wherein the pyridine bisimine is selected from the group consisting of 2,6-bis[(phenylimine) methyljpyridine, 2,6-bis[(2- methylphenylimine)methyl]pyridine, 2,6-bis[(2-ethylphenylimine)methyl]pyridine, 2,6-bis[(2- isopropylphenylimine)methyl]pyridine, 2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine, 2,6-bis[(2,6-diethylphenylimine)methyl]pyridine, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)- methyl] pyridine, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridine, and 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butyl
  • Embodiment 19 The process of embodiment 1 1, wherein the heteroatomic ligand or the heteroatomic ligand of the heteroatomic ligand metal salt complex is the phenanthroline imine and the phenanthroline imine comprises a 2-(hydrocarbylimine)-l, 10-phenanthroline, a 2-
  • Embodiment 20 The process of embodiment 19, wherein the phenanthroline imine comprises a 2-(2,6-dialkylphenylimine)- 1 , 10-phenanthroline, a 2-[(2,6-dialkylphenylimine)alkyl] -1, 10-phenan- throline, a 2-[(2,6-dialkylphenylimine)phenyl]- 1,10-phenanthroline, a 2-(2,4,6-trialkylphenylimine)-l, 10- phenanthroline, a 2-[(2,4,6-trialkylphenylimine)alkyl]-l,10-phenanthroline, a 2-[(2,4,6- trialkylphenylimine)phenyl]- 1,10-phenanthroline, a 2-(2,6-dihalophenylimine)- 1, 10-phenanthroline, a 2- [(2,6-dihalophenylimine)alkyl] -1, 10-phenanthroline, and
  • Embodiment 21 The process of embodiment 19, wherein phenanthroline imine is selected from the group consisting of 2-(2,6-difluorophenylimine)- 1, 10-phenanthroline, 2-(2,6- dichlorophenylimine)- 1 , 10-phenanthroline, 2-(2,6-dibromophenylimine)- 1 , 10-phenanthroline, 2-(2,6- dimethylphenylimine)- 1 , 10-phenanthroline, 2-(2,6-diethylphenylimine)- 1 , 10-phenanthroline, 2-(2,6- diisopropylphenylimine)- 1 , 10-phenanthroline, 2- [(2,6-difluorophenylimine)methyl] -1, 10-phenanthroline, 2-[(2,6-dichlorophenylimine)m ethyl] -1,10-phenanthroline, 2-[(2,6-dibromophenylimine)methyl] -1,
  • Embodiment 22 The process of any one of embodiments 1 to 21, wherein the organoaluminum compound comprises an aluminoxane.
  • Embodiment 23 The process of embodiment 22, wherein the aluminoxane comprises methylaluminoxane, a modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso- propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane, 1 -pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof.
  • Embodiment 24 The process of any one of embodiments 1 to 23, wherein the organo groups of the organoaluminum compound are substantially devoid of ⁇ , ⁇ -branched organo groups and/or ⁇ , ⁇ - branched organo groups.
  • Embodiment 25 The process of any one of embodiments 1 to 24, wherein the oligomer product is formed under conditions having (or the reaction zone has) an heteroatomic ligand molar equivalent concentration or heteroatomic ligand metal salt complex molar equivalent concentration of at least 1 x 10 "6 mmol/kg (or any other heteroatomic ligand molar equivalent concentration or heteroatomic ligand metal salt complex molar equivalent concentration disclosed herein).
  • Embodiment 26 The process of any one of embodiments 1 to 25, wherein the oligomer product is formed under conditions having (or the reaction zone has) an aluminum of the organo aluminum compound to heteroatomic ligand molar equivalent ratio or aluminum to heteroatomic ligand metal salt complex molar equivalent ratio of at least 100: 1 (or any other aluminum to heteroatomic ligand molar equivalent ratio or aluminum to heteroatomic ligand metal salt complex molar equivalent ratio disclosed herein).
  • Embodiment 27 The process of any one of embodiments 1 to 26, wherein the oligomer product is formed under conditions having (or the reaction zone has) an aluminum of the organoaluminum compound concentration of at least 0.3 mmol Al/kg (or any other aluminum of the organoaluminum compound concentration disclosed herein).
  • Embodiment 28 The process of any one of embodiments 1 to 27, wherein the oligomer product is formed under conditions having (or the reaction zone has) an ethylene partial pressure of at least 100 psi (or any other ethylene partial pressure disclosed herein.
  • Embodiment 29 The process of any one of embodiments 1 to 28, wherein the oligomer product is formed under conditions having (or the reaction zone has) a temperature of at least 0 °C (or any other temperature disclosed herein).
  • Embodiment 30 The process of any one of embodiments 1 to 29, wherein the process utilizes a hydrogen and the oligomer product is formed under conditions having (or the reaction zone has) a hydrogen partial pressure of at least 5 psi (or any other hydrogen partial pressure disclosed herein).
  • Embodiment 31 The process of any one of embodiments 1 to 30, wherein the process utilizes a hydrogen and the oligomer product is formed under conditions having (or the reaction zone has) a hydrogen to ethylene mass ratio of at least (0.05 g hydrogen)/(kg ethylene) (or any other hydrogen to ethylene mass ratio disclosed herein).
  • Embodiment 32 The process of any one of embodiments 1 to 31, wherein the process utilizes an organic reaction medium and the organic reaction medium comprises, or consists essentially of, one or more aliphatic hydrocarbons.
  • Embodiment 33 The process of embodiments 32, wherein the organic reaction medium comprises, or consists essentially of, one or more C 8 to Cig aliphatic hydrocarbons.
  • Embodiment 34 The process of embodiments 32, wherein the organic reaction medium comprises, or consists essentially of, one or more C 8 to Ci 6 saturated aliphatic hydrocarbons.
  • Embodiment 35 The process of embodiments 32, wherein the organic reaction medium comprises, or consists essentially of, one or more C 8 to Ci 6 olefinic aliphatic hydrocarbons.
  • Embodiment 36 The process of embodiments 32, wherein the organic reaction medium comprises, or consists essentially of, 1-decene, 1-dodecene, 1-tetradecene, or any combination thereof.
  • Embodiment 37 The process of any one of embodiments 32 to 36, wherein the organic reaction medium is substantially devoid of a halogenated compound.
  • Embodiment 38 The process of any one of embodiments 32 to 37, wherein the oligomer product is formed under conditions having (or the reaction zone has) an ethylene to organic reaction medium mass ratio of at least 0.8: 1 (or any other ethylene to organic reaction medium mass ratio disclosed herein),
  • Embodiment 39 The process of any one of embodiments 1 to 38, wherein the oligomer product has a Schultz-Flory K value in the range of 0.4 to 0.9 (or any other Schultz-Flory K value disclosed herein).
  • Heteroatomic metal salt complex ADIFe XIV was prepared using methods disclosed in US 2007/00221608 Al .
  • Heteroatomic ligand PBI 1 was prepared using methods disclosed in US 2002/0016425 Al .
  • Ethylene oligomerization runs using no additional metal salt and additional metal salt, Fe(acac) 2 were run in pairs on the same day utilizing the same reactor to allow for comparison between the ethylene oligomerization runs performed on the same day.
  • a stock toluene solution of 2.0 mg/mL (2.53 x 10 "3 meq/mL) of ADIFe XIV and a stock toluene solution of 4.0 mg/mL (1.57 x 10 "2 meq/mL) of Fe(acac) 2 were prepared.
  • the appropriate amount of the ADIFe XIV and the Fe(acac) 2 stock solutions were added to a 5 mL NMR tube to provide the desired quantity of ADIFe XIV and of Fe(acac) 2 for the ethylene oligomerization.
  • the NMR tube was then sealed.
  • a glass charger was charged with 200 mL cyclohexane, approximately 1.0 g of n-nonane internal standard, and the appropriate amount of MMAO-7 (Akzo Nobel, 7.0 wt% Al) to achieve the desired a-diimine ligand to aluminum molar ratio for the ethylene oligomerization.
  • the glass charger was then sealed.
  • the NMR tube and charger were removed from the drybox.
  • the NMR tube was secured to the stirrer shaft of a 1000 mL autoclave reactor with wire in a manner where the glass would shatter on starting the mixer.
  • the autoclave reactor was then sealed and evacuated under high vacuum.
  • the glass charger was then affixed to a charging port on the top of the autoclave reactor. After evacuating the reactor for several minutes, the entire contents of the glass charger were loaded into the autoclave reactor under vacuum.
  • the autoclave reactor was then degassed with ethylene by carrying out several fill/vent cycles.
  • the reactor was then pressurized with ethylene to 400 psig (2.8 MPa). Stirring was initiated resulting in breakage of the 5 mm NMR tube and activation of the catalyst.
  • Ethylene was then fed to the autoclave reactor on demand to maintain a pressure of 400 psig (2.8 MPa) for the remainder of the reaction.
  • the reaction temperature was maintained at a temperature of 50 to 60 °C by way of cooling water passed through internal cooling coils inside the autoclave reactor. After 15 min, the reactor was cooled to room temperature and vented to atmospheric pressure.
  • the liquid products were analyzed by a gas chromatograph with a flame ionization detector (FID) detector against the n-nonane internal standard. Table 1 details the results of these ethylene oligomerization examples.
  • Ethylene oligomerization examples 1 and 2 were run on the same day, while ethylene oligomerization examples 3 and 4 were run on a different day, and ethylene oligomerization examples 5 and 6 were run on yet a different day.
  • a glass charger was charged with 200 mL cyclohexane, approximately 1.0 g of n-nonane internal standard, and the appropriate amount of MMAO-3A (Akzo Nobel, 7.0 wt% Al) to achieve the desired PBI 1 to aluminum molar ratio for the ethylene oligomerization.
  • the glass charger was then sealed.
  • the NMR tube and charger were removed from the drybox.
  • the NMR tube was secured to the stirrer shaft of a 1000 mL autoclave reactor with wire in a manner where the glass would shatter on starting the mixer.
  • the autoclave reactor was then sealed and evacuated under high vacuum.
  • the glass charger was then affixed to a charging port on the top of the autoclave reactor.
  • heteroatomic ligand iron dichloride 2-[(2,6-diethylphenylimine)methyl-l,10- phenanthroline iron dichloride (PhenlFe 1) is prepared using the procedures disclosed in CN 104418690 A.
  • a stock toluene solution of 1.0 mg/mL (4.15 x 10 "3 meq/mL) of PhenlFe 1 and a stock toluene solution 4.0 mg/mL (1.57 x 10 "2 meq/mL) of Fe(acac) 2 are prepared.
  • the appropriate amount of the PhenlFe 1 and of the Fe(acac) 2 stock solutions are added to a 5 mL NMR tube to provide the desired quantity of PhenlFe 1 and of Fe(acac) 2 for the ethylene oligomerization.
  • the NMR tube is then sealed.
  • a glass charger is charged with 100 mL cyclohexane, approximately 1.0 g of n-nonane internal standard, and the appropriate amount of MMAO-7 (Akzo Nobel, 7.0 wt% Al) to achieve the desired a-diimine ligand to aluminum molar ratio for the ethylene oligomerization.
  • the glass charger is then sealed.
  • the NMR tube and glass charger are then removed from the drybox.
  • the NMR tube is secured to the stirrer shaft of a 500 mL autoclave reactor with wire in a manner where the glass will shatter on starting the mixer.
  • the autoclave reactor is then sealed and evacuated under high vacuum.
  • the glass charger is then affixed to a charging port on the top of the autoclave reactor. After evacuating the reactor for several minutes, the entire contents of the glass charger is loaded into the autoclave reactor under vacuum.
  • the autoclave reactor is then degassed with ethylene by carrying out several fill/vent cycles.
  • the reactor is then pressurized with ethylene to 400 psig (2.8 MPa). Stirring is initiated resulting in breakage of the 5 mm NMR tube and activation of the catalyst.
  • Ethylene is then fed to the autoclave reactor on demand to maintain a pressure of 400 psig (2.8 MPa) for the remainder of the reaction.
  • the reaction temperature is maintained at a temperature of 60 to 70 °C by way of cooling water passed through internal cooling coils inside the autoclave reactor.
  • Example 1 One ethylene oligomerization (Example 1 1) is performed in the absence of added Fe(acac) 2 and a second ethylene oligomerization (Example 12) is performed using a 10: 1 molar ratio of Fe(acac) 2 to PhenlFe 1.
  • the ethylene oligomerization performed with 10: 1 molar ratio of Fe(acac) 2 to PhenlFe 1 produces an oligomer product which has productivity (in g (C 4 -C 20 )/mmol PhenlFe 1) 20 % greater than the productivity of the ethylene oligomerization performed without added Fe(acac) 2 .
  • productivity in g (C 4 -C 20 )/mmol PhenlFe 1
  • heteroatomic ligand iron dichloride 2-[(2,6-diethylphenylimine)methyl-l, 10- phenanthroline (Phenl 1) is prepared using the procedures disclosed in CN 104418690 A.
  • a stock cyclohexane solution of 0.13 mg/mL (3.65 x 10 "3 meq/mL) of Phenl 1 and a stock cyclohexane solution 1.0 mg/mL (3.94 x 10 "3 meq/mL) of Fe(acac) 2 are prepared.
  • the appropriate amount of the Phenl 1 and the Fe(acac) 2 stock solutions are added to a 5 mL NMR tube to provide the desired quantity of Phenl 1 and of Fe(acac) 2 for the ethylene oligomerization.
  • the NMR tube is then sealed.
  • a glass charger is charged with 200 mL cyclohexane, approximately 1.0 g of n-nonane internal standard, and the appropriate amount of MMAO-7 (Akzo Nobel, 7.0 wt% Al) to achieve the desired a-diimine ligand to aluminum molar ratio for the ethylene oligomerization.
  • the glass charger is then sealed.
  • the NMR tube and glass charger are then removed from the drybox.
  • the NMR tube is secured to the stirrer shaft of a 1000 mL autoclave reactor with wire in a manner where the glass will shatter on starting the mixer.
  • the autoclave reactor is then sealed and evacuated under high vacuum.
  • the glass charger is then affixed to a charging port on the top of the autoclave reactor. After evacuating the reactor for several minutes, the entire contents of the glass charger are loaded into the autoclave reactor under vacuum.
  • the autoclave reactor is then degassed with ethylene by carrying out several fill/vent cycles.
  • the reactor is then pressurized with ethylene to 400 psig (2.8 MPa). Stirring is initiated resulting in breakage of the 5 mm NMR tube and activation of the catalyst.
  • Ethylene is then fed to the autoclave reactor on demand to maintain a pressure of 400 psig (2.8 MPa) for the remainder of the reaction.
  • the reaction temperature is maintained at a temperature of 60 to 70 °C by way of cooling water passed through internal cooling coils inside the autoclave reactor.
  • the reactor is cooled to room temperature and vented to atmospheric pressure.
  • the liquid products are analyzed by a gas chromatograph with a flame ionization detector (FID) detector against the n-nonane internal standard.
  • the first ethylene oligomerization (Example 13) is performed with a 1 : 1 Fe(acac) 2 to Phenl 1 molar ratio.
  • the second ethylene oligomerization (Example 14) is performed with a 5: 1 Fe(acac) 2 to Phenl 1 molar ratio.
  • the third ethylene oligomerization (Example 15) is performed with a 10: 1 Fe(acac) 2 to Phenl 1 molar ratio.
  • the ethylene oligomerization performed with 5: 1 molar ratio of Fe(acac) 2 to Phenl 1 produces an oligomer product which has productivity (in g (C 4 -C 20 )/mmol Phenl 1) over 400 % greater than the productivity of the ethylene oligomerization performed with a 1 : 1 molar ratio of Fe(acac) 2 to Phenl 1.
  • the ethylene oligomerization performed with 10: 1 molar ratio of Fe(acac) 2 to Phenl 1 produces an oligomer product which has productivity (in g (C 4 -C 20 )/mmol Phenl 1) over 600 % greater than the productivity of the ethylene oligomerization performed with a 1 : 1 molar ratio of Fe(acac) 2 to Phenl 1.

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Abstract

L'invention concerne un procédé de formation d'un produit oligomère consistant à (a) introduire dans une zone de réaction (i) l'éthylène ; (ii) un complexe de sel métallique de ligand hétéroatomique comprenant un ligand hétéroatomique complexé à un premier sel métallique ; (iii) un second sel métallique dans lequel un rapport molaire équivalent du second sel métallique au ligand hétéroatomique du complexe hétéroatomique de sel métallique est d'au moins 0,5 : 1 et le second sel métallique étant un sel de fer, un sel de cobalt, ou n'importe quelle combinaison de ceux-ci ; (iv) un composé d'organoaluminium ; et (b) former un produit oligomère. L'invention concerne également un procédé consistant à (a) introduire dans une zone de réaction (i) l'éthylène ; (ii) un ligand hétéroatomique ; (iii) un sel métallique dans lequel un rapport molaire équivalent du sel métallique au ligand hétéroatomique est d'au moins 1,5 : 1 ; (iv) un composé d'organoaluminium ; et (b) former un produit oligomère.
PCT/US2017/068281 2016-12-29 2017-12-22 Procédés d'oligomérisation d'éthylène WO2018125826A1 (fr)

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EP17832164.2A EP3562799B1 (fr) 2016-12-29 2017-12-22 Procédés d'oligomérisation d'éthylène
CN201780080378.9A CN110099884B (zh) 2016-12-29 2017-12-22 乙烯低聚方法

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US15/394,411 US20180186708A1 (en) 2016-12-29 2016-12-29 Ethylene Oligomerization Processes
US15/394,317 2016-12-29
US15/394,317 US10604457B2 (en) 2016-12-29 2016-12-29 Ethylene oligomerization processes
US15/394,411 2016-12-29
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US15/852,623 US10407360B2 (en) 2017-12-22 2017-12-22 Ethylene oligomerization processes

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US10544070B2 (en) 2017-12-22 2020-01-28 Chevron Phillips Chemical Company, Lp Ethylene oligomerization process
WO2022132866A1 (fr) * 2020-12-15 2022-06-23 Shell Oil Company Procédé de production d'alpha-oléfines
CN115400800A (zh) * 2022-09-22 2022-11-29 中化泉州石化有限公司 一种乙烯选择性三聚催化剂组合物及其应用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10544070B2 (en) 2017-12-22 2020-01-28 Chevron Phillips Chemical Company, Lp Ethylene oligomerization process
WO2022132866A1 (fr) * 2020-12-15 2022-06-23 Shell Oil Company Procédé de production d'alpha-oléfines
CN115400800A (zh) * 2022-09-22 2022-11-29 中化泉州石化有限公司 一种乙烯选择性三聚催化剂组合物及其应用
CN115400800B (zh) * 2022-09-22 2023-12-22 中化泉州石化有限公司 一种乙烯选择性三聚催化剂组合物及其应用

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