Methods of making an alkene from a polymer

Abstract

Disclosed herein, inter alia, are methods of making alkenes from a polymer and dehydrogenated polyethylene compositions.

Description

METHODS OF MAKING AN ALKENE FROM A POLYMER CROSS-REFERENCES TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application Nos.63 / 389,591 filed July 15, 2022 and 63 / 407,055 filed September 15, 2022, the disclosures of which are incorporated herein by reference in their entireties and for all purposes. STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT

[0002] This invention was made with government support under Grant Number DE-AC02- 05CH11231 awarded by the Department of Energy. The government has certain rights in the invention. BACKGROUND

[0003] The conversion of polyolefins to small molecules (e.g., monomers) would enable the largest fraction of waste plastic to be a carbon feedstock, but such a task requires cleavage of carbon-carbon bonds that often resist selective chemical transformations. Disclosed herein, inter alia, are solutions to these and other problems in the art. BRIEF SUMMARY

[0004] In an aspect is provided a method of making an alkene, the method including mixing a dehydrogenated polymer with one or more olefin metathesis reagent(s). In embodiments, the method includes mixing a dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s). In embodiments, the dehydrogenated polymer includes at most 10% unsaturated alkene monomer units. In embodiments, the dehydrogenated polymer includes at least 20 carbon atoms. In embodiments, prior to the mixing, the method includes mixing a polymer with one or more dehydrogenating reagent(s), thereby forming the dehydrogenated polymer. In embodiments, the method includes mixing a dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s); wherein: (i) the dehydrogenated polymer includes at most 10% unsaturated alkene monomer units; (ii) the dehydrogenated polymer includes at least 20 carbon atoms; or (iii) prior to themixing, the method includes mixing a polymer with one or more dehydrogenating reagent(s), thereby forming the dehydrogenated polymer.

[0005] In an aspect is provided a method of making a dehydrogenated polymer, the method including mixing a polymer with one or more dehydrogenating reagent(s), wherein: (i) a percentage of from 0.01% to 1.5% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 1.7% to 2.3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 2.4% to 4.3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 4.5% to 13.2% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, the method includes mixing a polymer with one or more dehydrogenating reagent(s), wherein: (i) a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units in the dehydrogenated polymer are unsaturated; (ii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da or greater; (iii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da and a percentage of 0.01% to 10% of monomer units are unsaturated; or (iv) the dehydrogenated polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 100 Da to about 2,200 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da or greater. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da.

[0006] In an aspect is provided a method of degrading a substance, the method including: (i) conducting one or more reaction(s) to form one or more olefin units in the substance; (ii) subjecting, after step (i), to conditions for olefin metathesis; and (iii) subjecting, after step (i), to conditions for olefin isomerization.

[0007] In an aspect is provided a method of making a substituted or unsubstituted alkene, the method including subjecting a dehydrogenated polymer to conditions for metathesis and to conditions for olefin isomerization.

[0008] In an aspect is provided a method of making a substituted or unsubstituted alkene, the method comprising subjecting a first substance to conditions for metathesis and to conditions for olefin isomerization; wherein: (i) the first substance includes at least 20 carbon atoms per molecule; or (ii) prior to subjecting the first substance to conditions for metathesis and to conditions for olefin isomerization, the method includes subjecting a second substance to conditions for dehydrogenation, thereby forming the first substance.

[0009] In an aspect is provided a substituted or unsubstituted dehydrogenated polyethylene, wherein a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units are unsaturated (e.g., olefinic, e.g., monoenes). In embodiments, a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units are olefinic. In embodiments, a percentage of from 0.01% to 1.5% of monomer units are olefinic. In embodiments, a percentage of from 1.7% to 2.3% of monomer units are olefinic. In embodiments, a percentage of from 1.7% to 2.3% of monomer units are olefinic. In embodiments, a percentage of from 2.4% to 4.3% of monomer units are olefinic. In embodiments, a percentage of from 4.5% to 13.2% of monomer units are olefinic.

[0010] In an aspect is provided a substituted or unsubstituted dehydrogenated polyethylene, having a number average molecular weight of 2,200 Da or greater. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] FIGS.1A-1D. Strategies for the valorization of PE waste. FIG.1A: Degradation of PE by alkane metathesis with n-hexane (Huang 2016, Román-Leshkov 2021). FIG.1B: Conversion of PE to alkyl aromatics by tandem hydrogenolysis / aromatization (Scott 2020). FIG.1C: Degradation of PE by hydrogenolysis. FIG.1D: Conversion of PE to propene by DIE (x = number of IE turnovers).

[0012] FIGS.2A-2D. Conditions tested for DIE. FIG.2A: Homogeneous dehydrogenation of PE. Conditions for dehydrogenation: 0.42 mol % Ir-tBuPOCOP, 0.46 mol % NaOtBu, 0.6M in PE,reactions run for 12 h with 0.4 equiv TBE (mol %, equiv TBE, and M of PE calculated relative to PE monomer units). FIG.2B: Heterogeneous dehydrogenation of PE (HDPE, Mn = 26.1 kDa) with bimetallic catalysts supported on alumina. Conditions: 20 wt % catalyst, 350 °C. Catalysts were first activated under H2 flow for 1 h, then dehydrogenation was run for 16 h under Ar flow. FIG.2C: GPC Chromatogram of HDPE prior to and after ethenolysis with M-1. Conditions for ethenolysis were: 0.36 M in unsaturated PE 3.6 mol% M-1 in p-xylene, heated to 130 °C for 16 h under 25 bar ethylene. FIG.2D: Sequential dehydrogenation and ethenolysis of a long chain paraffin (C24H50). Initial dehydrogenation yields olefins in 10% yield, and subsequent ethenolysis with M-1 yields a statistical distribution of shorter-chain olefins.

[0013] FIGS.3A-3C. Development of conditions for DIE of PE. FIG.3A: Optimization of catalyst combinations for IE of 1-octadecene. Conditions: 1-octadecene (0.5 M) was combined with isomerization (3.0 mol%) and metathesis (6.0 mol%) catalysts in p-xylene and heated to 60 °C under 25 bar of ethylene for 16 h. (a) I-2 (6 mol%) was combined with Pd(OAc)2(3 mol%) and methanesulfonic acid (30 mol%) to generate the active isomerization catalyst (25). The reaction was also conducted in THF to ensure catalyst solubility. (b) I-3 was activated by the addition of 1.5 equiv HBPin relative to I-3 (also conducted in THF for catalyst solubility). FIG. 3B: Application of IE to dehydro-polyethylene, with dehydro-HDPE yielding a maximum of 80% propene with 1.96% dehydrogenation. Conditions for IE of dehydrogenated PE: 3.6% M-1, 2.2% I-1, 1.78 M in PE, heated to 130 °C in p-xylene for 16 h under 25 bar of ethylene. FIG. 3C: DIE of13C-labeled HDPE to check for background reactivity (conditions identical to those in FIG.3B).

[0014] FIG.4. DIE of post-consumer PE (conditions identical to those in FIG.3B). Propene yields are reported as XX%(YY) where X is the yield obtained from polymer purified by precipitation from acetone, and Y is the yield obtained from unmodified polymer. Where a single yield is reported, dehydrogenation on unpurified samples failed. From left to right: Recycled HDPE (rHDPE) sourced from can tops; HDPE sourced from a milk jug; HDPE sourced from a shampoo bottle; LDPE sourced from food packaging.

[0015] FIGS.5A-5E. Investigation of reaction scope and kinetics. FIG.5A: Time course of IE with 1-octadecene (100% Yield= 458.3mBar). FIG.5B: Time course of IE with dehydrogenated HDPE (1.41% Olefin) (100% Yield = 193.5mBar). FIG.5C: Yields of IE onsmall molecules 1a-1d designed to assess the effect of branching on IE. FIG.5D: Yields of IE on small molecules 1e-1f designed to test the effect of dienes on IE. FIG.5E: Experiments utilizing poly(cyclooctene) PCO (Mn= designed to demonstrate the effect of polymer unsaturation on IE yield, in the absence of branching. Conditions for IE in FIGS.5C-5E identical to those in FIG.3C. DETAILED DESCRIPTION I. Definitions

[0016] The abbreviations used herein have their conventional meaning within the chemical and biological arts. The chemical structures and formulae set forth herein are constructed according to the standard rules of chemical valency known in the chemical arts.

[0017] Where substituent groups are specified by their conventional chemical formulae, written from left to right, they equally encompass the chemically identical substituents that would result from writing the structure from right to left, e.g., -CH2O- is equivalent to -OCH2-.

[0018] The term “alkyl,” by itself or as part of another substituent, means, unless otherwise stated, a straight (i.e., unbranched) or branched carbon chain (or carbon), or combination thereof, which may be fully saturated, mono- or polyunsaturated and can include mono-, di-, and multivalent radicals. The alkyl may include a designated number of carbons (e.g., C1-C10means one to ten carbons). Alkyl is an uncyclized chain. Examples of saturated hydrocarbon radicals include, but are not limited to, groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, methyl, homologs and isomers of, for example, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like. An unsaturated alkyl group is one having one or more double bonds or triple bonds. Examples of unsaturated alkyl groups include, but are not limited to, vinyl, 2- propenyl, crotyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl, and the higher homologs and isomers. An alkoxy is an alkyl attached to the remainder of the molecule via an oxygen linker (-O-). An alkyl moiety may be an alkenyl moiety. An alkyl moiety may be an alkynyl moiety. An alkyl moiety may be fully saturated. An alkenyl may include more than one double bond and / or one or more triple bonds in addition to the one or more double bonds. An alkynyl may include more than one triple bond and / or one or more double bonds in addition to the one or more triple bonds.

[0019] The term “alkylene,” by itself or as part of another substituent, means, unless otherwise stated, a divalent radical derived from an alkyl, as exemplified, but not limited by, -CH2CH2CH2CH2-. Typically, an alkyl (or alkylene) group will have from 1 to 24 carbon atoms, with those groups having 10 or fewer carbon atoms being preferred herein. A “lower alkyl” or “lower alkylene” is a shorter chain alkyl or alkylene group, generally having eight or fewer carbon atoms. The term “alkenylene,” by itself or as part of another substituent, means, unless otherwise stated, a divalent radical derived from an alkene. The term “alkynylene” by itself or as part of another substituent, means, unless otherwise stated, a divalent radical derived from an alkyne.

[0020] The term “heteroalkyl,” by itself or in combination with another term, means, unless otherwise stated, a stable straight or branched chain, or combinations thereof, including at least one carbon atom and at least one heteroatom (e.g., O, N, P, Si, and S), and wherein the nitrogen and sulfur atoms may optionally be oxidized, and the nitrogen heteroatom may optionally be quaternized. The heteroatom(s) (e.g., O, N, S, Si, or P) may be placed at any interior position of the heteroalkyl group or at the position at which the alkyl group is attached to the remainder of the molecule. Heteroalkyl is an uncyclized chain. Examples include, but are not limited to: -CH2-CH2-O-CH3, -CH2-CH2-NH-CH3, -CH2-CH2-N(CH3)-CH3, -CH2-S-CH2-CH3, -CH2-S-CH2, -S(O)-CH3, -CH2-CH2-S(O)2-CH3, -CH=CH-O-CH3, -Si(CH3)3, -CH2-CH=N-OCH3, -CH=CH-N(CH3)-CH3, -O-CH3, -O-CH2-CH3, and -CN. Up to two or three heteroatoms may be consecutive, such as, for example, -CH2-NH-OCH3and -CH2-O-Si(CH3)3. A heteroalkyl moiety may include one heteroatom (e.g., O, N, S, Si, or P). A heteroalkyl moiety may include two optionally different heteroatoms (e.g., O, N, S, Si, or P). A heteroalkyl moiety may include three optionally different heteroatoms (e.g., O, N, S, Si, or P). A heteroalkyl moiety may include four optionally different heteroatoms (e.g., O, N, S, Si, or P). A heteroalkyl moiety may include five optionally different heteroatoms (e.g., O, N, S, Si, or P). A heteroalkyl moiety may include up to 8 optionally different heteroatoms (e.g., O, N, S, Si, or P). The term “heteroalkenyl,” by itself or in combination with another term, means, unless otherwise stated, a heteroalkyl including at least one double bond. A heteroalkenyl may optionally include more than one double bond and / or one or more triple bonds in additional to the one or more double bonds. The term “heteroalkynyl,” by itself or in combination with another term, means, unless otherwise stated, a heteroalkyl including at least one triple bond. A heteroalkynyl mayoptionally include more than one triple bond and / or one or more double bonds in additional to the one or more triple bonds.

[0021] Similarly, the term “heteroalkylene,” by itself or as part of another substituent, means, unless otherwise stated, a divalent radical derived from heteroalkyl, as exemplified, but not limited by, -CH2-CH2-S-CH2-CH2- and -CH2-S-CH2-CH2-NH-CH2-. For heteroalkylene groups, heteroatoms can also occupy either or both of the chain termini (e.g., alkyleneoxy, alkylenedioxy, alkyleneamino, alkylenediamino, and the like). Still further, for alkylene and heteroalkylene linking groups, no orientation of the linking group is implied by the direction in which the formula of the linking group is written. For example, the formula -C(O)2R'- represents both -C(O)2R'- and -R'C(O)2-. As described above, heteroalkyl groups, as used herein, include those groups that are attached to the remainder of the molecule through a heteroatom, such as -C(O)R', -C(O)NR', -NR'R'', -OR', -SR', and / or -SO2R'. Where “heteroalkyl” is recited, followed by recitations of specific heteroalkyl groups, such as -NR'R'' or the like, it will be understood that the terms heteroalkyl and -NR'R'' are not redundant or mutually exclusive. Rather, the specific heteroalkyl groups are recited to add clarity. Thus, the term “heteroalkyl” should not be interpreted herein as excluding specific heteroalkyl groups, such as -NR'R'' or the like.

[0022] The terms “cycloalkyl” and “heterocycloalkyl,” by themselves or in combination with other terms, mean, unless otherwise stated, cyclic versions of “alkyl” and “heteroalkyl,” respectively. Cycloalkyl and heterocycloalkyl are not aromatic. Additionally, for heterocycloalkyl, a heteroatom can occupy the position at which the heterocycle is attached to the remainder of the molecule. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-cyclohexenyl, 3-cyclohexenyl, cycloheptyl, and the like. Examples of heterocycloalkyl include, but are not limited to, 1-(1,2,5,6- tetrahydropyridyl), 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-morpholinyl, 3-morpholinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, 1- piperazinyl, 2-piperazinyl, and the like. A “cycloalkylene” and a “heterocycloalkylene,” alone or as part of another substituent, means a divalent radical derived from a cycloalkyl and heterocycloalkyl, respectively.

[0023] In embodiments, the term “cycloalkyl” means a monocyclic, bicyclic, or a multicyclic cycloalkyl ring system. In embodiments, monocyclic ring systems are cyclic hydrocarbongroups containing from 3 to 8 carbon atoms, where such groups can be saturated or unsaturated, but not aromatic. In embodiments, cycloalkyl groups are fully saturated. Examples of monocyclic cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, and cyclooctyl. Bicyclic cycloalkyl ring systems are bridged monocyclic rings or fused bicyclic rings. In embodiments, bridged monocyclic rings contain a monocyclic cycloalkyl ring where two non adjacent carbon atoms of the monocyclic ring are linked by an alkylene bridge of between one and three additional carbon atoms (i.e., a bridging group of the form (CH2)w, where w is 1, 2, or 3). Representative examples of bicyclic ring systems include, but are not limited to, bicyclo[3.1.1]heptane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, bicyclo[3.2.2]nonane, bicyclo[3.3.1]nonane, and bicyclo[4.2.1]nonane. In embodiments, fused bicyclic cycloalkyl ring systems contain a monocyclic cycloalkyl ring fused to either a phenyl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, a monocyclic heterocyclyl, or a monocyclic heteroaryl. In embodiments, the bridged or fused bicyclic cycloalkyl is attached to the parent molecular moiety through any carbon atom contained within the monocyclic cycloalkyl ring. In embodiments, cycloalkyl groups are optionally substituted with one or two groups which are independently oxo or thia. In embodiments, the fused bicyclic cycloalkyl is a 5 or 6 membered monocyclic cycloalkyl ring fused to either a phenyl ring, a 5 or 6 membered monocyclic cycloalkyl, a 5 or 6 membered monocyclic cycloalkenyl, a 5 or 6 membered monocyclic heterocyclyl, or a 5 or 6 membered monocyclic heteroaryl, wherein the fused bicyclic cycloalkyl is optionally substituted by one or two groups which are independently oxo or thia. In embodiments, multicyclic cycloalkyl ring systems are a monocyclic cycloalkyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of a phenyl, a bicyclic aryl, a monocyclic or bicyclic heteroaryl, a monocyclic or bicyclic cycloalkyl, a monocyclic or bicyclic cycloalkenyl, and a monocyclic or bicyclic heterocyclyl. In embodiments, the multicyclic cycloalkyl is attached to the parent molecular moiety through any carbon atom contained within the base ring. In embodiments, multicyclic cycloalkyl ring systems are a monocyclic cycloalkyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two other ring systems independentlyselected from the group consisting of a phenyl, a monocyclic heteroaryl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, and a monocyclic heterocyclyl. Examples of multicyclic cycloalkyl groups include, but are not limited to tetradecahydrophenanthrenyl, perhydrophenothiazin-1-yl, and perhydrophenoxazin-1-yl.

[0024] In embodiments, a cycloalkyl is a cycloalkenyl. The term “cycloalkenyl” is used in accordance with its plain ordinary meaning. In embodiments, a cycloalkenyl is a monocyclic, bicyclic, or a multicyclic cycloalkenyl ring system. In embodiments, monocyclic cycloalkenyl ring systems are cyclic hydrocarbon groups containing from 3 to 8 carbon atoms, where such groups are unsaturated (i.e., containing at least one annular carbon carbon double bond), but not aromatic. Examples of monocyclic cycloalkenyl ring systems include cyclopentenyl and cyclohexenyl. In embodiments, bicyclic cycloalkenyl rings are bridged monocyclic rings or a fused bicyclic rings. In embodiments, bridged monocyclic rings contain a monocyclic cycloalkenyl ring where two non adjacent carbon atoms of the monocyclic ring are linked by an alkylene bridge of between one and three additional carbon atoms (i.e., a bridging group of the form (CH2)w, where w is 1, 2, or 3). Representative examples of bicyclic cycloalkenyls include, but are not limited to, norbornenyl and bicyclo[2.2.2]oct 2 enyl. In embodiments, fused bicyclic cycloalkenyl ring systems contain a monocyclic cycloalkenyl ring fused to either a phenyl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, a monocyclic heterocyclyl, or a monocyclic heteroaryl. In embodiments, the bridged or fused bicyclic cycloalkenyl is attached to the parent molecular moiety through any carbon atom contained within the monocyclic cycloalkenyl ring. In embodiments, cycloalkenyl groups are optionally substituted with one or two groups which are independently oxo or thia. In embodiments, multicyclic cycloalkenyl rings contain a monocyclic cycloalkenyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two ring systems independently selected from the group consisting of a phenyl, a bicyclic aryl, a monocyclic or bicyclic heteroaryl, a monocyclic or bicyclic cycloalkyl, a monocyclic or bicyclic cycloalkenyl, and a monocyclic or bicyclic heterocyclyl. In embodiments, the multicyclic cycloalkenyl is attached to the parent molecular moiety through any carbon atom contained within the base ring. In embodiments, multicyclic cycloalkenyl rings contain a monocyclic cycloalkenyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic cycloalkyl, a bicycliccycloalkenyl, and a bicyclic heterocyclyl; or (ii) two ring systems independently selected from the group consisting of a monocyclic cycloalkyl, a monocyclic cycloalkenyl, and a monocyclic heterocyclyl.

[0025] In embodiments, a heterocycloalkyl is a heterocyclyl. The term “heterocyclyl” as used herein, means a monocyclic, bicyclic, or multicyclic heterocycle. The heterocyclyl monocyclic heterocycle is a 3, 4, 5, 6 or 7 membered ring containing at least one heteroatom independently selected from the group consisting of O, N, and S where the ring is saturated or unsaturated, but not aromatic. The 3 or 4 membered ring contains 1 heteroatom selected from the group consisting of O, N, and S. The 5 membered ring can contain zero or one double bond and one, two or three heteroatoms selected from the group consisting of O, N, and S. The 6 or 7 membered ring contains zero, one or two double bonds and one, two or three heteroatoms selected from the group consisting of O, N, and S. The heterocyclyl monocyclic heterocycle is connected to the parent molecular moiety through any carbon atom or any nitrogen atom contained within the heterocyclyl monocyclic heterocycle. Representative examples of heterocyclyl monocyclic heterocycles include, but are not limited to, azetidinyl, azepanyl, aziridinyl, diazepanyl, 1,3-dioxanyl, 1,3-dioxolanyl, 1,3-dithiolanyl, 1,3-dithianyl, imidazolinyl, imidazolidinyl, isothiazolinyl, isothiazolidinyl, isoxazolinyl, isoxazolidinyl, morpholinyl, oxadiazolinyl, oxadiazolidinyl, oxazolinyl, oxazolidinyl, piperazinyl, piperidinyl, pyranyl, pyrazolinyl, pyrazolidinyl, pyrrolinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, thiadiazolinyl, thiadiazolidinyl, thiazolinyl, thiazolidinyl, thiomorpholinyl, 1,1- dioxidothiomorpholinyl (thiomorpholine sulfone), thiopyranyl, and trithianyl. The heterocyclyl bicyclic heterocycle is a monocyclic heterocycle fused to either a phenyl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, a monocyclic heterocycle, or a monocyclic heteroaryl. The heterocyclyl bicyclic heterocycle is connected to the parent molecular moiety through any carbon atom or any nitrogen atom contained within the monocyclic heterocycle portion of the bicyclic ring system. Representative examples of bicyclic heterocyclyls include, but are not limited to, 2,3-dihydrobenzofuran-2-yl, 2,3-dihydrobenzofuran-3-yl, indolin-1-yl, indolin-2-yl, indolin-3-yl, 2,3-dihydrobenzothien-2-yl, decahydroquinolinyl, decahydroisoquinolinyl, octahydro-1H-indolyl, and octahydrobenzofuranyl. In embodiments, heterocyclyl groups are optionally substituted with one or two groups which are independently oxo or thia. In certain embodiments, the bicyclic heterocyclyl is a 5 or 6 membered monocyclic heterocyclyl ring fusedto a phenyl ring, a 5 or 6 membered monocyclic cycloalkyl, a 5 or 6 membered monocyclic cycloalkenyl, a 5 or 6 membered monocyclic heterocyclyl, or a 5 or 6 membered monocyclic heteroaryl, wherein the bicyclic heterocyclyl is optionally substituted by one or two groups which are independently oxo or thia. Multicyclic heterocyclyl ring systems are a monocyclic heterocyclyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of a phenyl, a bicyclic aryl, a monocyclic or bicyclic heteroaryl, a monocyclic or bicyclic cycloalkyl, a monocyclic or bicyclic cycloalkenyl, and a monocyclic or bicyclic heterocyclyl. The multicyclic heterocyclyl is attached to the parent molecular moiety through any carbon atom or nitrogen atom contained within the base ring. In embodiments, multicyclic heterocyclyl ring systems are a monocyclic heterocyclyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of a phenyl, a monocyclic heteroaryl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, and a monocyclic heterocyclyl. Examples of multicyclic heterocyclyl groups include, but are not limited to 10H-phenothiazin-10-yl, 9,10- dihydroacridin-9-yl, 9,10-dihydroacridin-10-yl, 10H-phenoxazin-10-yl, 10,11-dihydro-5H- dibenzo[b,f]azepin-5-yl, 1,2,3,4-tetrahydropyrido[4,3-g]isoquinolin-2-yl, 12H- benzo[b]phenoxazin-12-yl, and dodecahydro-1H-carbazol-9-yl.

[0026] The terms “halo” or “halogen,” by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom. Additionally, terms such as “haloalkyl” are meant to include monohaloalkyl and polyhaloalkyl. For example, the term “halo(C1-C4)alkyl” includes, but is not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 4-chlorobutyl, 3-bromopropyl, and the like.

[0027] The term “acyl” means, unless otherwise stated, -C(O)R where R is a substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0028] The term “aryl” means, unless otherwise stated, a polyunsaturated, aromatic, hydrocarbon substituent, which can be a single ring or multiple rings (preferably from 1 to 3 rings) that are fused together (i.e., a fused ring aryl) or linked covalently. A fused ring aryl refers to multiple rings fused together wherein at least one of the fused rings is an aryl ring. The term “heteroaryl” refers to aryl groups (or rings) that contain at least one heteroatom such as N, O, or S, wherein the nitrogen and sulfur atoms are optionally oxidized, and the nitrogen atom(s) are optionally quaternized. Thus, the term “heteroaryl” includes fused ring heteroaryl groups (i.e., multiple rings fused together wherein at least one of the fused rings is a heteroaromatic ring). A 5,6-fused ring heteroarylene refers to two rings fused together, wherein one ring has 5 members and the other ring has 6 members, and wherein at least one ring is a heteroaryl ring. Likewise, a 6,6-fused ring heteroarylene refers to two rings fused together, wherein one ring has 6 members and the other ring has 6 members, and wherein at least one ring is a heteroaryl ring. And a 6,5- fused ring heteroarylene refers to two rings fused together, wherein one ring has 6 members and the other ring has 5 members, and wherein at least one ring is a heteroaryl ring. A heteroaryl group can be attached to the remainder of the molecule through a carbon or heteroatom. Non- limiting examples of aryl and heteroaryl groups include phenyl, naphthyl, pyrrolyl, pyrazolyl, pyridazinyl, triazinyl, pyrimidinyl, imidazolyl, pyrazinyl, purinyl, oxazolyl, isoxazolyl, thiazolyl, furyl, thienyl, pyridyl, pyrimidyl, benzothiazolyl, benzoxazoyl benzimidazolyl, benzofuran, isobenzofuranyl, indolyl, isoindolyl, benzothiophenyl, isoquinolyl, quinoxalinyl, quinolyl, 1- naphthyl, 2-naphthyl, 4-biphenyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 2-imidazolyl, 4- imidazolyl, pyrazinyl, 2-oxazolyl, 4-oxazolyl, 2-phenyl-4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4- isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-furyl, 3-furyl, 2-thienyl, 3- thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-benzothiazolyl, purinyl, 2- benzimidazolyl, 5-indolyl, 1-isoquinolyl, 5-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 3- quinolyl, and 6-quinolyl. Substituents for each of the above noted aryl and heteroaryl ring systems are selected from the group of acceptable substituents described below. An “arylene” and a “heteroarylene,” alone or as part of another substituent, mean a divalent radical derived from an aryl and heteroaryl, respectively. A heteroaryl group substituent may be -O- bonded to a ring heteroatom nitrogen.

[0029] A fused ring heterocyloalkyl-aryl is an aryl fused to a heterocycloalkyl. A fused ring heterocycloalkyl-heteroaryl is a heteroaryl fused to a heterocycloalkyl. A fused ringheterocycloalkyl-cycloalkyl is a heterocycloalkyl fused to a cycloalkyl. A fused ring heterocycloalkyl-heterocycloalkyl is a heterocycloalkyl fused to another heterocycloalkyl. Fused ring heterocycloalkyl-aryl, fused ring heterocycloalkyl-heteroaryl, fused ring heterocycloalkyl- cycloalkyl, or fused ring heterocycloalkyl-heterocycloalkyl may each independently be unsubstituted or substituted with one or more of the substitutents described herein.

[0030] Spirocyclic rings are two or more rings wherein adjacent rings are attached through a single atom. The individual rings within spirocyclic rings may be identical or different. Individual rings in spirocyclic rings may be substituted or unsubstituted and may have different substituents from other individual rings within a set of spirocyclic rings. Possible substituents for individual rings within spirocyclic rings are the possible substituents for the same ring when not part of spirocyclic rings (e.g., substituents for cycloalkyl or heterocycloalkyl rings). Spirocylic rings may be substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heterocycloalkyl or substituted or unsubstituted heterocycloalkylene and individual rings within a spirocyclic ring group may be any of the immediately previous list, including having all rings of one type (e.g., all rings being substituted heterocycloalkylene wherein each ring may be the same or different substituted heterocycloalkylene). When referring to a spirocyclic ring system, heterocyclic spirocyclic rings means a spirocyclic rings wherein at least one ring is a heterocyclic ring and wherein each ring may be a different ring. When referring to a spirocyclic ring system, substituted spirocyclic rings means that at least one ring is substituted and each substituent may optionally be different.

[0031] The symbol “ ” denotes the point of attachment of a chemical moiety to the remainder of a molecule or chemical formula.

[0032] The term “oxo,” as used herein, means an oxygen that is double bonded to a carbon atom.

[0033] The term “alkylarylene” as an arylene moiety covalently bonded to an alkylene moiety (also referred to herein as an alkylene linker). In embodiments, the alkylarylene group has the formula:.

[0034] An alkylarylene moiety may be substituted (e.g., with a substituent group) on the alkylene moiety or the arylene linker (e.g., at carbons 2, 3, 4, or 6) with halogen, oxo, -N3, -CF3, -CCl3, -CBr3, -CI3, -CN, -C(O)H, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO2CH3, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, substituted or unsubstituted C1- C5alkyl or substituted or unsubstituted 2 to 5 membered heteroalkyl). In embodiments, the alkylarylene is unsubstituted.

[0035] The term “alkylsulfonyl,” as used herein, means a moiety having the formula -S(O2)-R', where R' is a substituted or unsubstituted alkyl group as defined above. R' may have a specified number of carbons (e.g., “C1-C4 alkylsulfonyl”).

[0036] Each of the above terms (e.g., “alkyl,” “heteroalkyl,” “cycloalkyl,” “heterocycloalkyl,” “aryl,” and “heteroaryl”) includes both substituted and unsubstituted forms of the indicated radical. Preferred substituents for each type of radical are provided below.

[0037] Substituents for the alkyl and heteroalkyl radicals (including those groups often referred to as alkylene, alkenyl, heteroalkylene, heteroalkenyl, alkynyl, cycloalkyl, heterocycloalkyl, cycloalkenyl, and heterocycloalkenyl) can be one or more of a variety of groups selected from, but not limited to, -OR', =O, =NR', =N-OR', -NR'R'', -SR', -halogen, -SiR'R''R''', -OC(O)R', -C(O)R', -CO2R', -CONR'R'', -OC(O)NR'R'', -NR''C(O)R', -NR'-C(O)NR''R''', -NR''C(O)2R', -NR-C(NR'R''R''')=NR'''', -NR-C(NR'R'')=NR''', -S(O)R', -S(O)2R', -S(O)2NR'R'', -NRSO2R', ^NR'NR''R''', ^ONR'R'', ^NR'C(O)NR''NR'''R'''', -CN, -NO2, -NR'SO2R'', -NR'C(O)R'', -NR'C(O)OR'', -NR'OR'', in a number ranging from zero to (2m'+1), where m' is the total number of carbon atoms in such radical. R, R', R'', R''', and R'''' each preferably independently refer to hydrogen, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl (e.g., aryl substituted with 1-3 halogens), substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, alkoxy, or thioalkoxy groups, or arylalkyl groups. When a compound described herein includes more than one R group, for example, each of the R groups is independently selected as are each R', R'', R''', and R'''' group when more than one of thesegroups is present. When R' and R'' are attached to the same nitrogen atom, they can be combined with the nitrogen atom to form a 4-, 5-, 6-, or 7-membered ring. For example, -NR'R'' includes, but is not limited to, 1-pyrrolidinyl and 4-morpholinyl. From the above discussion of substituents, one of skill in the art will understand that the term “alkyl” is meant to include groups including carbon atoms bound to groups other than hydrogen groups, such as haloalkyl (e.g., -CF3and -CH2CF3) and acyl (e.g., -C(O)CH3, -C(O)CF3, -C(O)CH2OCH3, and the like).

[0038] Similar to the substituents described for the alkyl radical, substituents for the aryl and heteroaryl groups are varied and are selected from, for example: -OR', -NR'R'', -SR', -halogen, -SiR'R''R''', -OC(O)R', -C(O)R', -CO2R', -CONR'R'', -OC(O)NR'R'', -NR''C(O)R', -NR'-C(O)NR''R''', -NR''C(O)2R', -NR-C(NR'R''R''')=NR'''', -NR-C(NR'R'')=NR''', -S(O)R', -S(O)2R', -S(O)2NR'R'', -NRSO2R', ^NR'NR''R''', ^ONR'R'', ^NR'C(O)NR''NR'''R'''', -CN, -NO2, -R', -N3, -CH(Ph)2, fluoro(C1-C4)alkoxy, and fluoro(C1-C4)alkyl, -NR'SO2R'', -NR'C(O)R'', -NR'C(O)-OR'', -NR'OR'', in a number ranging from zero to the total number of open valences on the aromatic ring system; and where R', R'', R''', and R'''' are preferably independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl. When a compound described herein includes more than one R group, for example, each of the R groups is independently selected as are each R', R'', R''', and R'''' groups when more than one of these groups is present.

[0039] Substituents for rings (e.g., cycloalkyl, heterocycloalkyl, aryl, heteroaryl, cycloalkylene, heterocycloalkylene, arylene, or heteroarylene) may be depicted as substituents on the ring rather than on a specific atom of a ring (commonly referred to as a floating substituent). In such a case, the substituent may be attached to any of the ring atoms (obeying the rules of chemical valency) and in the case of fused rings or spirocyclic rings, a substituent depicted as associated with one member of the fused rings or spirocyclic rings (a floating substituent on a single ring), may be a substituent on any of the fused rings or spirocyclic rings (a floating substituent on multiple rings). When a substituent is attached to a ring, but not a specific atom (a floating substituent), and a subscript for the substituent is an integer greater than one, the multiple substituents may be on the same atom, same ring, different atoms, different fused rings, different spirocyclic rings, and each substituent may optionally be different. Where a point ofattachment of a ring to the remainder of a molecule is not limited to a single atom (a floating substituent), the attachment point may be any atom of the ring and in the case of a fused ring or spirocyclic ring, any atom of any of the fused rings or spirocyclic rings while obeying the rules of chemical valency. Where a ring, fused rings, or spirocyclic rings contain one or more ring heteroatoms and the ring, fused rings, or spirocyclic rings are shown with one more floating substituents (including, but not limited to, points of attachment to the remainder of the molecule), the floating substituents may be bonded to the heteroatoms. Where the ring heteroatoms are shown bound to one or more hydrogens (e.g., a ring nitrogen with two bonds to ring atoms and a third bond to a hydrogen) in the structure or formula with the floating substituent, when the heteroatom is bonded to the floating substituent, the substituent will be understood to replace the hydrogen, while obeying the rules of chemical valency.

[0040] Two or more substituents may optionally be joined to form aryl, heteroaryl, cycloalkyl, or heterocycloalkyl groups. Such so-called ring-forming substituents are typically, though not necessarily, found attached to a cyclic base structure. In one embodiment, the ring-forming substituents are attached to adjacent members of the base structure. For example, two ring- forming substituents attached to adjacent members of a cyclic base structure create a fused ring structure. In another embodiment, the ring-forming substituents are attached to a single member of the base structure. For example, two ring-forming substituents attached to a single member of a cyclic base structure create a spirocyclic structure. In yet another embodiment, the ring- forming substituents are attached to non-adjacent members of the base structure.

[0041] Two of the substituents on adjacent atoms of the aryl or heteroaryl ring may optionally form a ring of the formula -T-C(O)-(CRR')q-U-, wherein T and U are independently -NR-, -O-, -CRR'-, or a single bond, and q is an integer of from 0 to 3. Alternatively, two of the substituents on adjacent atoms of the aryl or heteroaryl ring may optionally be replaced with a substituent of the formula -A-(CH2)r-B-, wherein A and B are independently -CRR'-, -O-, -NR-, -S-, -S(O) -, -S(O)2-, -S(O)2NR'-, or a single bond, and r is an integer of from 1 to 4. One of the single bonds of the new ring so formed may optionally be replaced with a double bond. Alternatively, two of the substituents on adjacent atoms of the aryl or heteroaryl ring may optionally be replaced with a substituent of the formula -(CRR')s-X'- (C''R''R''')d-, where s and d are independently integers of from 0 to 3, and X' is -O-, -NR'-, -S-, -S(O)-, -S(O)2-, or -S(O)2NR'-. The substituents R, R',R'', and R''' are preferably independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.

[0042] As used herein, the terms “heteroatom” or “ring heteroatom” are meant to include oxygen (O), nitrogen (N), sulfur (S), phosphorus (P), and silicon (Si).

[0043] A “substituent group,” as used herein, means a group selected from the following moieties: (A) oxo, halogen, -CCl3, -CBr3, -CF3, -CI3, CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, -N3, unsubstituted alkyl (e.g., C1-C8 alkyl, C1-C6alkyl, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered heteroalkyl, 2 to 6 membered heteroalkyl, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8 cycloalkyl, C3-C6 cycloalkyl, or C5-C6 cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered heterocycloalkyl, 3 to 6 membered heterocycloalkyl, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10aryl, C10 aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered heteroaryl, 5 to 9 membered heteroaryl, or 5 to 6 membered heteroaryl), and (B) alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5- C6), heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), aryl (e.g., C6-C12, C6-C10, or phenyl), or heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered), substituted with at least one substituent selected from: (i) oxo, halogen, -CCl3, -CBr3, -CF3, -CI3, CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H,-OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, -N3, unsubstituted alkyl (e.g., C1-C8alkyl, C1-C6alkyl, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered heteroalkyl, 2 to 6 membered heteroalkyl, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8 cycloalkyl, C3-C6 cycloalkyl, or C5- C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered heterocycloalkyl, 3 to 6 membered heterocycloalkyl, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10 aryl, C10 aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered heteroaryl, 5 to 9 membered heteroaryl, or 5 to 6 membered heteroaryl), and (ii) alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), aryl (e.g., C6-C12, C6-C10, or phenyl), or heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered), substituted with at least one substituent selected from: (a) oxo, halogen, -CCl3, -CBr3, -CF3, -CI3, CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, -N3, unsubstituted alkyl (e.g., C1-C8 alkyl, C1-C6 alkyl, or C1-C4 alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered heteroalkyl, 2 to 6 membered heteroalkyl, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8cycloalkyl, C3-C6cycloalkyl, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered heterocycloalkyl, 3 to 6 membered heterocycloalkyl, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10aryl, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered heteroaryl, 5 to 9 membered heteroaryl, or 5 to 6 membered heteroaryl), and(b) alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), aryl (e.g., C6-C12, C6-C10, or phenyl), or heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered), substituted with at least one substituent selected from: oxo, halogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, -N3, unsubstituted alkyl (e.g., C1-C8 alkyl, C1-C6 alkyl, or C1-C4 alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered heteroalkyl, 2 to 6 membered heteroalkyl, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8cycloalkyl, C3-C6cycloalkyl, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered heterocycloalkyl, 3 to 6 membered heterocycloalkyl, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6- C10aryl, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered heteroaryl, 5 to 9 membered heteroaryl, or 5 to 6 membered heteroaryl).

[0044] A “size-limited substituent” or “ size-limited substituent group,” as used herein, means a group selected from all of the substituents described above for a “substituent group,” wherein each substituted or unsubstituted alkyl is a substituted or unsubstituted C1-C20 alkyl, each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2 to 20 membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3-C8cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3 to 8 membered heterocycloalkyl, each substituted or unsubstituted aryl is a substituted or unsubstituted C6-C10aryl, and each substituted or unsubstituted heteroaryl is a substituted or unsubstituted 5 to 10 membered heteroaryl.

[0045] A “lower substituent” or “ lower substituent group,” as used herein, means a group selected from all of the substituents described above for a “substituent group,” wherein each substituted or unsubstituted alkyl is a substituted or unsubstituted C1-C8alkyl, each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2 to 8 membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3-C7 cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3 to 7 membered heterocycloalkyl, each substituted or unsubstituted aryl is a substituted or unsubstituted phenyl, and each substituted or unsubstituted heteroaryl is a substituted or unsubstituted 5 to 6 membered heteroaryl.

[0046] In some embodiments, each substituted group described in the compounds herein is substituted with at least one substituent group. More specifically, in some embodiments, each substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and / or substituted heteroarylene described in the compounds herein are substituted with at least one substituent group. In other embodiments, at least one or all of these groups are substituted with at least one size-limited substituent group. In other embodiments, at least one or all of these groups are substituted with at least one lower substituent group.

[0047] In other embodiments of the compounds herein, each substituted or unsubstituted alkyl may be a substituted or unsubstituted C1-C20alkyl, each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2 to 20 membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3-C8 cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3 to 8 membered heterocycloalkyl, each substituted or unsubstituted aryl is a substituted or unsubstituted C6-C10 aryl, and / or each substituted or unsubstituted heteroaryl is a substituted or unsubstituted 5 to 10 membered heteroaryl. In some embodiments of the compounds herein, each substituted or unsubstituted alkylene is a substituted or unsubstituted C1-C20alkylene, each substituted or unsubstituted heteroalkylene is a substituted or unsubstituted 2 to 20 membered heteroalkylene, each substituted or unsubstituted cycloalkylene is a substituted or unsubstituted C3-C8cycloalkylene, each substituted or unsubstituted heterocycloalkylene is a substituted or unsubstituted 3 to 8membered heterocycloalkylene, each substituted or unsubstituted arylene is a substituted or unsubstituted C6-C10 arylene, and / or each substituted or unsubstituted heteroarylene is a substituted or unsubstituted 5 to 10 membered heteroarylene.

[0048] In some embodiments, each substituted or unsubstituted alkyl is a substituted or unsubstituted C1-C8 alkyl, each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2 to 8 membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3-C7cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3 to 7 membered heterocycloalkyl, each substituted or unsubstituted aryl is a substituted or unsubstituted C6-C10 aryl, and / or each substituted or unsubstituted heteroaryl is a substituted or unsubstituted 5 to 9 membered heteroaryl. In some embodiments, each substituted or unsubstituted alkylene is a substituted or unsubstituted C1-C8 alkylene, each substituted or unsubstituted heteroalkylene is a substituted or unsubstituted 2 to 8 membered heteroalkylene, each substituted or unsubstituted cycloalkylene is a substituted or unsubstituted C3-C7 cycloalkylene, each substituted or unsubstituted heterocycloalkylene is a substituted or unsubstituted 3 to 7 membered heterocycloalkylene, each substituted or unsubstituted arylene is a substituted or unsubstituted C6-C10arylene, and / or each substituted or unsubstituted heteroarylene is a substituted or unsubstituted 5 to 9 membered heteroarylene. In some embodiments, the compound is a chemical species set forth in the application (e.g., Examples section, claims, embodiments, figures, or tables below).

[0049] In embodiments, a substituted or unsubstituted moiety (e.g., substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heterocycloalkylene, substituted or unsubstituted arylene, and / or substituted or unsubstituted heteroarylene) is unsubstituted (e.g., is an unsubstituted alkyl, unsubstituted heteroalkyl, unsubstituted cycloalkyl, unsubstituted heterocycloalkyl, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted alkylene, unsubstituted heteroalkylene, unsubstituted cycloalkylene, unsubstituted heterocycloalkylene, unsubstituted arylene, and / or unsubstituted heteroarylene, respectively). In embodiments, a substituted or unsubstituted moiety (e.g., substituted or unsubstituted alkyl,substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heterocycloalkylene, substituted or unsubstituted arylene, and / or substituted or unsubstituted heteroarylene) is substituted (e.g., is a substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and / or substituted heteroarylene, respectively).

[0050] In embodiments, a substituted moiety (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and / or substituted heteroarylene) is substituted with at least one substituent group, wherein if the substituted moiety is substituted with a plurality of substituent groups, each substituent group may optionally be different. In embodiments, if the substituted moiety is substituted with a plurality of substituent groups, each substituent group is different.

[0051] In embodiments, a substituted moiety (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and / or substituted heteroarylene) is substituted with at least one size-limited substituent group, wherein if the substituted moiety is substituted with a plurality of size-limited substituent groups, each size-limited substituent group may optionally be different. In embodiments, if the substituted moiety is substituted with a plurality of size-limited substituent groups, each size-limited substituent group is different.

[0052] In embodiments, a substituted moiety (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and / or substituted heteroarylene) is substituted with at least one lower substituent group, wherein if the substituted moiety is substituted with a pluralityof lower substituent groups, each lower substituent group may optionally be different. In embodiments, if the substituted moiety is substituted with a plurality of lower substituent groups, each lower substituent group is different.

[0053] In embodiments, a substituted moiety (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and / or substituted heteroarylene) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted moiety is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size- limited substituent group, and / or lower substituent group may optionally be different. In embodiments, if the substituted moiety is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group is different.

[0054] In a recited claim or chemical formula description herein, each R substituent or L linker that is described as being “substituted” without reference as to the identity of any chemical moiety that composes the “substituted” group (also referred to herein as an “open substitution” on an R substituent or L linker or an “openly substituted” R substituent or L linker), the recited R substituent or L linker may, in embodiments, be substituted with one or more first substituent groups as defined below.

[0055] The first substituent group is denoted with a corresponding first decimal point numbering system such that, for example, R1may be substituted with one or more first substituent groups denoted by R1.1, R2may be substituted with one or more first substituent groups denoted by R2.1, R3may be substituted with one or more first substituent groups denoted by R3.1, R4may be substituted with one or more first substituent groups denoted by R4.1, R5may be substituted with one or more first substituent groups denoted by R5.1, and the like up to or exceeding an R100that may be substituted with one or more first substituent groups denoted by R100.1. As a further example, R1Amay be substituted with one or more first substituent groups denoted by R1A.1, R2Amay be substituted with one or more first substituent groups denoted by R2A.1, R3Amay be substituted with one or more first substituent groups denoted by R3A.1, R4Amay be substituted with one or more first substituent groups denoted by R4A.1, R5Amay be substituted with one or more first substituent groups denoted by R5A.1and the like up to or exceeding an R100Amay be substituted with one or more first substituent groups denoted by R100A.1. As a further example, L1may be substituted with one or more first substituent groups denoted by RL1.1, L2may be substituted with one or more first substituent groups denoted by RL2.1, L3may be substituted with one or more first substituent groups denoted by RL3.1, L4may be substituted with one or more first substituent groups denoted by RL4.1, L5may be substituted with one or more first substituent groups denoted by RL5.1and the like up to or exceeding an L100which may be substituted with one or more first substituent groups denoted by RL100.1. Thus, each numbered R group or L group (alternatively referred to herein as RWWor LWWwherein “WW” represents the stated superscript number of the subject R group or L group) described herein may be substituted with one or more first substituent groups referred to herein generally as RWW.1or RLWW.1, respectively. In turn, each first substituent group (e.g., R1.1, R2.1, R3.1, R4.1, R5.1… R100.1; R1A.1, R2A.1, R3A.1, R4A.1, R5A.1… R100A.1; RL1.1, RL2.1, RL3.1, RL4.1, RL5.1… RL100.1) may be further substituted with one or more second substituent groups (e.g., R1.2, R2.2, R3.2, R4.2, R5.2… R100.2; R1A.2, R2A.2, R3A.2, R4A.2, R5A.2… R100A.2; RL1.2, RL2.2, RL3.2, RL4.2, RL5.2… RL100.2, respectively). Thus, each first substituent group, which may alternatively be represented herein as RWW.1as described above, may be further substituted with one or more second substituent groups, which may alternatively be represented herein as RWW.2.

[0056] Finally, each second substituent group (e.g., R1.2, R2.2, R3.2, R4.2, R5.2… R100.2; R1A.2, R2A.2, R3A.2, R4A.2, R5A.2… R100A.2; RL1.2, RL2.2, RL3.2, RL4.2, RL5.2… RL100.2) may be further substituted with one or more third substituent groups (e.g., R1.3, R2.3, R3.3, R4.3, R5.3… R100.3; R1A.3, R2A.3, R3A.3, R4A.3, R5A.3… R100A.3; RL1.3, RL2.3, RL3.3, RL4.3, RL5.3… RL100.3; respectively). Thus, each second substituent group, which may alternatively be represented herein as RWW.2as described above, may be further substituted with one or more third substituent groups, which may alternatively be represented herein as RWW.3. Each of the first substituent groups may be optionally different. Each of the second substituent groups may be optionally different. Each of the third substituent groups may be optionally different.

[0057] Thus, as used herein, RWWrepresents a substituent recited in a claim or chemical formula description herein which is openly substituted. “WW” represents the stated superscriptnumber of the subject R group (1, 2, 3, 1A, 2A, 3A, 1B, 2B, 3B, etc.). Likewise, LWWis a linker recited in a claim or chemical formula description herein which is openly substituted. Again, “WW” represents the stated superscript number of the subject L group (1, 2, 3, 1A, 2A, 3A, 1B, 2B, 3B, etc.). As stated above, in embodiments, each RWWmay be unsubstituted or independently substituted with one or more first substituent groups, referred to herein as RWW.1; each first substituent group, RWW.1, may be unsubstituted or independently substituted with one or more second substituent groups, referred to herein as RWW.2; and each second substituent group may be unsubstituted or independently substituted with one or more third substituent groups, referred to herein as RWW.3. Similarly, each LWWlinker may be unsubstituted or independently substituted with one or more first substituent groups, referred to herein as RLWW.1; each first substituent group, RLWW.1, may be unsubstituted or independently substituted with one or more second substituent groups, referred to herein as RLWW.2; and each second substituent group may be unsubstituted or independently substituted with one or more third substituent groups, referred to herein as RLWW.3. Each first substituent group is optionally different. Each second substituent group is optionally different. Each third substituent group is optionally different. For example, if RWWis phenyl, the said phenyl group is optionally substituted by one or more RWW.1groups as defined herein below, e.g., when RWW.1is RWW.2-substituted or unsubstituted alkyl, examples of groups so formed include but are not limited to itself optionally substituted by 1 or more RWW.2, which RWW.2is optionally substituted by one or more RWW.3. By way of example when the RWWgroup is phenyl substituted by RWW.1, which is methyl, the methyl group may be further substituted to form groups including but not limited to:.

[0058] RWW.1is independently oxo, halogen, -CXWW.13, -CHXWW.12, -CH2XWW.1, -OCXWW.13, -OCH2XWW.1, -OCHXWW.12, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, RWW.2-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), RWW.2-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), RWW.2-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), RWW.2-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), RWW.2-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or RWW.2-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, RWW.1is independently oxo, halogen, -CXWW.13, -CHXWW.12, -CH2XWW.1, -OCXWW.13, -OCH2XWW.1, -OCHXWW.12, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g.,5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). XWW.1is independently –F, -Cl, -Br, or –I.

[0059] RWW.2is independently oxo, halogen, -CXWW.23, -CHXWW.22, -CH2XWW.2, -OCXWW.23, -OCH2XWW.2, -OCHXWW.22, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, RWW.3-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), RWW.3-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), RWW.3-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), RWW.3-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), RWW.3-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or RWW.3-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, RWW.2is independently oxo, halogen, -CXWW.23, -CHXWW.22, -CH2XWW.2, -OCXWW.23, -OCH2XWW.2, -OCHXWW.22, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). XWW.2is independently –F, -Cl, -Br, or –I.

[0060] RWW.3is independently oxo, halogen, -CXWW.33, -CHXWW.32, -CH2XWW.3, -OCXWW.33, -OCH2XWW.3, -OCHXWW.32, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). XWW.3is independently –F, -Cl, -Br, or –I.

[0061] Where two different RWWsubstituents are joined together to form an openly substituted ring (e.g., substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl or substituted heteroaryl), in embodiments the openly substituted ring may be independently substituted with one or more first substituent groups, referred to herein as RWW.1; each first substituent group, RWW.1, may be unsubstituted or independently substituted with one or more second substituent groups, referred to herein as RWW.2; and each second substituent group, RWW.2, may be unsubstituted or independently substituted with one or more third substituent groups, referred to herein as RWW.3; and each third substituent group, RWW.3, is unsubstituted. Each first substituent group is optionally different. Each second substituent group is optionally different. Each third substituent group is optionally different. In the context of two different RWWsubstituents joined together to form an openly substituted ring, the “WW” symbol in the RWW.1, RWW.2and RWW.3refers to the designated number of one of the two different RWWsubstituents. For example, in embodiments where R100Aand R100Bare optionally joined together to form an openly substituted ring, RWW.1is R100A.1, RWW.2is R100A.2, and RWW.3is R100A.3. Alternatively, in embodiments where R100Aand R100Bare optionally joined together to form an openly substituted ring, RWW.1is R100B.1, RWW.2is R100B.2, and RWW.3is R100B.3. RWW.1, RWW.2and RWW.3in this paragraph are as defined in the preceding paragraphs.

[0062] RLWW.1is independently oxo, halogen, -CXLWW.13, -CHXLWW.12, -CH2XLWW.1, -OCXLWW.13, -OCH2XLWW.1, -OCHXLWW.12, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, RLWW.2-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), RLWW.2-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), RLWW.2-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), RLWW.2-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), RLWW.2-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or RLWW.2-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, RLWW.1is independently oxo, halogen, -CXLWW.13, -CHXLWW.12, -CH2XLWW.1, -OCXLWW.13, -OCH2XLWW.1, -OCHXLWW.12, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). XLWW.1is independently –F, -Cl, -Br, or –I.

[0063] RLWW.2is independently oxo, halogen, -CXLWW.23, -CHXLWW.22, -CH2XLWW.2, -OCXLWW.23, -OCH2XLWW.2, -OCHXLWW.22, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, RLWW.3-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), RLWW.3-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), RWW.3-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), RLWW.3-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), RLWW.3-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or RLWW.3-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, RLWW.2is independently oxo, halogen, -CXLWW.23, -CHXLWW.22, -CH2XLWW.2, -OCXLWW.23, -OCH2XLWW.2, -OCHXLWW.22, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)-OH, -NHOH, -N3, unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g.,5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). XLWW.2is independently –F, -Cl, -Br, or –I.

[0064] RLWW.3is independently oxo, halogen, -CXLWW.33, -CHXLWW.32, -CH2XLWW.3, -OCXLWW.33, -OCH2XLWW.3, -OCHXLWW.32, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1- C2), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). XLWW.3is independently –F, -Cl, -Br, or –I.

[0065] In the event that any R group recited in a claim or chemical formula description set forth herein (RWWsubstituent) is not specifically defined in this disclosure, then that R group (RWWgroup) is hereby defined as independently oxo, halogen, -CXWW3, -CHXWW2, -CH2XWW, -OCXWW3, -OCH2XWW, -OCHXWW2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, RWW.1-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), RWW.1-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), RWW.1-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), RWW.1-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), RWW.1-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or RWW.1-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). XWWis independently –F, -Cl, -Br, or –I. Again, “WW” represents the stated superscript number of the subject R group (e.g., 1, 2, 3, 1A, 2A, 3A, 1B, 2B, 3B, etc.). RWW.1, RWW.2, and RWW.3are as defined above.

[0066] In the event that any L linker group recited in a claim or chemical formula description set forth herein (i.e., an LWWsubstituent) is not explicitly defined, then that L group (LWWgroup) is herein defined as independently a bond, –O-, -NH-, -C(O)-, -C(O)NH-, -NHC(O)-,-NHC(O)NH-, -C(O)O-, -OC(O)-, -S-, -SO2-, -SO2NH-, RLWW.1-substituted or unsubstituted alkylene (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), RLWW.1-substituted or unsubstituted heteroalkylene (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), RLWW.1-substituted or unsubstituted cycloalkylene (e.g., C3-C8, C3-C6, C4-C6, or C5- C6), RLWW.1-substituted or unsubstituted heterocycloalkylene (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), RLWW.1-substituted or unsubstituted arylene (e.g., C6-C12, C6-C10, or phenyl), or RLWW.1-substituted or unsubstituted heteroarylene (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). Again, “WW” represents the stated superscript number of the subject L group (1, 2, 3, 1A, 2A, 3A, 1B, 2B, 3B, etc.). RLWW.1, as well as RLWW.2and RLWW.3are as defined above.

[0067] Certain compounds of the present disclosure possess asymmetric carbon atoms (optical or chiral centers) or double bonds; the enantiomers, racemates, diastereomers, tautomers, geometric isomers, stereoisometric forms that may be defined, in terms of absolute stereochemistry, as (R)-or (S)- or, as (D)- or (L)- for amino acids, and individual isomers are encompassed within the scope of the present disclosure. The compounds of the present disclosure do not include those that are known in art to be too unstable to synthesize and / or isolate. The present disclosure is meant to include compounds in racemic and optically pure forms. Optically active (R)- and (S)-, or (D)- and (L)-isomers may be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. When the compounds described herein contain olefinic bonds or other centers of geometric asymmetry, and unless specified otherwise, it is intended that the compounds include both E and Z geometric isomers.

[0068] As used herein, the term “isomers” refers to compounds having the same number and kind of atoms, and hence the same molecular weight, but differing in respect to the structural arrangement or configuration of the atoms.

[0069] The term “tautomer,” as used herein, refers to one of two or more structural isomers which exist in equilibrium and which are readily converted from one isomeric form to another.

[0070] It will be apparent to one skilled in the art that certain compounds of this disclosure may exist in tautomeric forms, all such tautomeric forms of the compounds being within the scope of the disclosure.

[0071] Unless otherwise stated, structures depicted herein are also meant to include all stereochemical forms of the structure; i.e., the R and S configurations for each asymmetric center. Therefore, single stereochemical isomers as well as enantiomeric and diastereomeric mixtures of the present compounds are within the scope of the disclosure.

[0072] Unless otherwise stated, structures depicted herein are also meant to include compounds which differ only in the presence of one or more isotopically enriched atoms. For example, compounds having the present structures except for the replacement of a hydrogen by a deuterium or tritium, or the replacement of a carbon by13C- or14C-enriched carbon are within the scope of this disclosure.

[0073] The compounds of the present disclosure may also contain unnatural proportions of atomic isotopes at one or more of the atoms that constitute such compounds. For example, the compounds may be radiolabeled with radioactive isotopes, such as for example tritium (3H), iodine-125 (125I), or carbon-14 (14C). All isotopic variations of the compounds of the present disclosure, whether radioactive or not, are encompassed within the scope of the present disclosure.

[0074] It should be noted that throughout the application that alternatives are written in Markush groups, for example, each amino acid position that contains more than one possible amino acid. It is specifically contemplated that each member of the Markush group should be considered separately, thereby comprising another embodiment, and the Markush group is not to be read as a single unit.

[0075] “Analog” or “analogue” is used in accordance with its plain ordinary meaning within Chemistry and Biology and refers to a chemical compound that is structurally similar to another compound (i.e., a so-called “reference” compound) but differs in composition, e.g., in the replacement of one atom by an atom of a different element, or in the presence of a particular functional group, or the replacement of one functional group by another functional group, or the absolute stereochemistry of one or more chiral centers of the reference compound. Accordingly, an analog is a compound that is similar or comparable in function and appearance but not in structure or origin to a reference compound.

[0076] The terms “a” or “an”, as used in herein means one or more. In addition, the phrase “substituted with a[n]”, as used herein, means the specified group may be substituted with one or more of any or all of the named substituents. For example, where a group, such as an alkyl or heteroaryl group, is “substituted with an unsubstituted C1-C20 alkyl, or unsubstituted 2 to 20 membered heteroalkyl”, the group may contain one or more unsubstituted C1-C20 alkyls, and / or one or more unsubstituted 2 to 20 membered heteroalkyls.

[0077] Moreover, where a moiety is substituted with an R substituent, the group may be referred to as “R-substituted.” Where a moiety is R-substituted, the moiety is substituted with at least one R substituent and each R substituent is optionally different. Where a particular R group is present in the description of a chemical genus (such as Formula (I)), a Roman alphabetic symbol may be used to distinguish each appearance of that particular R group. For example, where multiple R13substituents are present, each R13substituent may be distinguished as R13A, R13B, R13C, R13D, etc., wherein each of R13A, R13B, R13C, R13D, etc. is defined within the scope of the definition of R13and optionally differently.

[0078] Radioactive substances (e.g., radioisotopes) that may be used as imaging and / or labeling agents in accordance with the embodiments of the disclosure include, but are not limited to,18F,32P,33P,45Ti,47Sc,52Fe,59Fe,62Cu,64Cu,67Cu,67Ga,68Ga,77As,86Y,90Y,89Sr,89Zr,94Tc,94Tc,99mTc,99Mo,105Pd,105Rh,111Ag,111In,123I,124I,125I,131I,142Pr,143Pr,149Pm,153Sm,154-1581Gd,161Tb,166Dy,166Ho,169Er,175Lu,177Lu,186Re,188Re,189Re,194Ir,198Au,199Au,211At,211Pb,212Pb,212Bi,213Bi,223Ra, and225Ac. Paramagnetic ions that may be used as additional imaging agents in accordance with the embodiments of the disclosure include, but are not limited to, ions of transition and lanthanide metals (e.g., metals having atomic numbers of 21-29, 42, 43, 44, or 57-71). These metals include ions of Cr, V, Mn, Fe, Co, Ni, Cu, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0079] Descriptions of compounds of the present disclosure are limited by principles of chemical bonding known to those skilled in the art. Accordingly, where a group may be substituted by one or more of a number of substituents, such substitutions are selected so as to comply with principles of chemical bonding and to give compounds which are not inherently unstable and / or would be known to one of ordinary skill in the art as likely to be unstable under ambient conditions, such as aqueous, neutral, and several known physiological conditions. Forexample, a heterocycloalkyl or heteroaryl is attached to the remainder of the molecule via a ring heteroatom in compliance with principles of chemical bonding known to those skilled in the art thereby avoiding inherently unstable compounds.

[0080] The term “leaving group” is used in accordance with its ordinary meaning in chemistry and refers to a moiety (e.g., atom, functional group, molecule) that separates from the molecule following a chemical reaction (e.g., bond formation, reductive elimination, condensation, cross- coupling reaction) involving an atom or chemical moiety to which the leaving group is attached, also referred to herein as the “leaving group reactive moiety”, and a complementary reactive moiety (i.e. a chemical moiety that reacts with the leaving group reactive moiety) to form a new bond between the remnants of the leaving groups reactive moiety and the complementary reactive moiety. Thus, the leaving group reactive moiety and the complementary reactive moiety form a complementary reactive group pair. Non limiting examples of leaving groups include hydrogen, hydroxide, organotin moieties (e.g., organotin heteroalkyl), halogen (e.g., Br), perfluoroalkylsulfonates (e.g. triflate), tosylates, mesylates, water, alcohols, nitrate, phosphate, thioether, amines, ammonia, fluoride, carboxylate, phenoxides, boronic acid, boronate esters, and alkoxides. In embodiments, two molecules with leaving groups are allowed to contact, and upon a reaction and / or bond formation (e.g., acyloin condensation, aldol condensation, Claisen condensation, Stille reaction) the leaving groups separates from the respective molecule.

[0081] A person of ordinary skill in the art will understand when a variable (e.g., moiety or linker) of a compound or of a compound genus (e.g., a genus described herein) is described by a name or formula of a standalone compound with all valencies filled, the unfilled valence(s) of the variable will be dictated by the context in which the variable is used. For example, when a variable of a compound as described herein is connected (e.g., bonded) to the remainder of the compound through a single bond, that variable is understood to represent a monovalent form (i.e., capable of forming a single bond due to an unfilled valence) of a standalone compound (e.g., if the variable is named “methane” in an embodiment but the variable is known to be attached by a single bond to the remainder of the compound, a person of ordinary skill in the art would understand that the variable is actually a monovalent form of methane, i.e., methyl or –CH3). Likewise, for a linker variable (e.g., L1, L2, or L3as described herein), a person of ordinary skill in the art will understand that the variable is the divalent form of a standalonecompound (e.g., if the variable is assigned to “PEG” or “polyethylene glycol” in an embodiment but the variable is connected by two separate bonds to the remainder of the compound, a person of ordinary skill in the art would understand that the variable is a divalent (i.e., capable of forming two bonds through two unfilled valences) form of PEG instead of the standalone compound PEG).

[0082] As used herein, the term “salt” refers to acid or base salts of the compounds used in the methods of the present invention. Illustrative examples of acceptable salts are mineral acid (hydrochloric acid, hydrobromic acid, phosphoric acid, and the like) salts, organic acid (acetic acid, propionic acid, glutamic acid, citric acid and the like) salts, quaternary ammonium (methyl iodide, ethyl iodide, and the like) salts.

[0083] Thus, the compounds of the present disclosure may exist as salts. The present disclosure includes such salts. Non-limiting examples of such salts include hydrochlorides, hydrobromides, phosphates, sulfates, methanesulfonates, nitrates, maleates, acetates, citrates, fumarates, proprionates, tartrates (e.g., (+)-tartrates, (-)-tartrates, or mixtures thereof including racemic mixtures), succinates, benzoates, and salts with amino acids such as glutamic acid, and quaternary ammonium salts (e.g., methyl iodide, ethyl iodide, and the like). These salts may be prepared by methods known to those skilled in the art.

[0084] The neutral forms of the compounds are preferably regenerated by contacting the salt with a base or acid and isolating the parent compound in the conventional manner. The parent form of the compound may differ from the various salt forms in certain physical properties, such as solubility in polar solvents.

[0085] Certain compounds of the present disclosure can exist in unsolvated forms as well as solvated forms, including hydrated forms. In general, the solvated forms are equivalent to unsolvated forms and are encompassed within the scope of the present disclosure. Certain compounds of the present disclosure may exist in multiple crystalline or amorphous forms. In general, all physical forms are equivalent for the uses contemplated by the present disclosure and are intended to be within the scope of the present disclosure.

[0086] As used herein, the term “about” means a range of values including the specified value, which a person of ordinary skill in the art would consider reasonably similar to the specifiedvalue. In embodiments, about means within a standard deviation using measurements generally acceptable in the art. In embodiments, about means a range extending to + / - 10% of the specified value. In embodiments, about includes the specified value.

[0087] “Contacting” is used in accordance with its plain ordinary meaning and refers to the process of allowing at least two distinct species (e.g., chemical compounds including biomolecules or cells) to become sufficiently proximal to react, interact or physically touch. It should be appreciated; however, the resulting reaction product can be produced directly from a reaction between the added reagents or from an intermediate from one or more of the added reagents that can be produced in the reaction mixture.

[0088] In this disclosure, “comprises,” “comprising,” “containing” and “having” and the like can have the meaning ascribed to them in U.S. Patent law and can mean “ includes,” “including,” and the like. “Consisting essentially of” or “consists essentially” likewise has the meaning ascribed in U.S. Patent law and the term is open-ended, allowing for the presence of more than that which is recited so long as basic or novel characteristics of that which is recited is not changed by the presence of more than that which is recited, but excludes prior art embodiments.

[0089] The term “polymer” is used in accordance with its plain ordinary meaning in the art, and refers to a molecule including repeating subunits (e.g., polymerized monomers).

[0090] The term “dehydrogenated polymer” as used herein refers to a polymer including a carbon-carbon double bond.

[0091] The term “olefin metathesis” is used in accordance with its plain ordinary meaning in the art, and refers to an organic reaction involving the redistribution of fragments of alkenes (olefins) by the scission and regeranation of carbon-carbon double bonds.

[0092] The term “olefin isomerization” is used in accordance with its plain ordinary meaning in the art, and refers to an organic reaction involving the relocation of a carbon-carbon double bond in a molecule to a different part of the molecule. In embodiments, olefin isomerization is isomerization of a terminal olefin to an internal olefin.

[0093] The term “dehydrogenation” is used in accordance with its plain ordinary meaning in the art, and refers to an organic reaction involving the removal of hydrogen, e.g., from an organic molecule. In embodiments, dehydrogenation is the conversion of an alkane to an olefin.

[0094] The term “catalyst” is used in accordance with its plain ordinary meaning in the art, and refers to a species that increases the rate of a chemical reaction. The catalyst is not consumed in the reaction and can continue to act repeatedly.

[0095] The term “high-density polyethylene” or “HDPE” refers to a thermoplastic polymer produced from the monomer ethylene and is known for its high strength-to-density ratio. Typically, the density of HDPE ranges from about 0.93 g / cm3to about 0.97 g / cm3. HDPE has minimal branching of its polymer chains and is therefore denser than low-density polyethylene.

[0096] The term “low-density polyethylene” or “LDPE” refers to a thermoplastic polymer produced from the monomer ethylene. Typically, the density of LDPE ranges from about 0.917 g / cm3to about 0.930 g / cm3.

[0097] The term “linear low-density polyethylene” or “LLDPE” refers to a substantially linear polyethylene with significant numbers of short branches. LLDPE differs from LDPE because of the absence of long chain branching. Typically, the density of LLDPE ranges from about 0.91 g / cm3to about 0.94 g / cm3. II. Methods

[0098] In an aspect is provided a method of degrading a substance, the method including: (i) conducting one or more reaction(s) to form one or more olefin units in the substance; (ii) subjecting, after step (i), to conditions for olefin metathesis; and (iii) subjecting, after step (i), to conditions for olefin isomerization. In embodiments, step (i) includes subjecting the substance to conditions for dehydrogenation.

[0099] In an aspect is provided a method of making a substituted or unsubstituted alkene, the method including subjecting a dehydrogenated polymer to conditions for olefin metathesis and to conditions for olefin isomerization.

[0100] In an aspect is provided a method of making a substituted or unsubstituted alkene, the method comprising subjecting a first substance to conditions for olefin metathesis and toconditions for olefin isomerization; wherein: (i) the first substance includes at least 20 carbon atoms per molecule; or (ii) prior to subjecting the first substance to conditions for olefin metathesis and to conditions for olefin isomerization, the method includes subjecting a second substance to conditions for dehydrogenation, thereby forming the first substance.

[0101] In an aspect is provided a method of making a substituted or unsubstituted alkene, the method comprising subjecting a first substance to conditions for olefin metathesis and to conditions for olefin isomerization; wherein: (i) the first substance includes at most 10% unsaturated alkene monomer units; (ii) the first substance includes at least 20 carbon atoms per molecule; or (iii) prior to subjecting the first substance to conditions for olefin metathesis and to conditions for olefin isomerization, the method includes subjecting a second substance to conditions for dehydrogenation, thereby forming the first substance.

[0102] In embodiments, the subjecting to conditions for olefin metathesis and subjecting to conditions for olefin isomerization are conducted simultaneously. In embodiments, the subjecting to conditions for olefin metathesis and subjecting to conditions for olefin isomerization are conducted simultaneously via orthogonal tandem catalysis.

[0103] In embodiments, the substance includes one or more polymers. In embodiments, the substance includes one polymer. In embodiments, the substance includes multiple polymers. In embodiments, the substance includes one or more polyolefins. In embodiments, the substance includes one polyolefin. In embodiments, the substance includes multiple polyolefins. In embodiments, the substance is a polyolefin.

[0104] In embodiments, the substance includes one or more polymers including one or more monomer units selected from ethylene units, propene units, 1-butene units, 2-butene units, isobutene units, 1-pentene units, 2-pentene units, 1-hexene units, 2-hexene units, 3-hexene units, 1-heptene units, 1-octene units, 1-nonene units, 1-decene units, styrene units, vinyl chloride units, vinyl fluoride units, cyclopentene units, cyclohexene units, cycloheptene units, cyclooctene units, cyclononane units, cyclodecene units, cycloundecene units, cyclododecene, and norbornene units. In embodiments, the substance includes one or more monomer units selected from ethylene, propene, styrene, and vinyl chloride. In embodiments, the substance includes one or more monomer units selected from ethylene and propene. In embodiments, the substance includes one or more monomer units selected from ethylene.

[0105] In embodiments, the substance includes one or more co-polymers including one or more monomer units selected from ethylene units, propene units, 1-butene units, 2-butene units, isobutene units, 1-pentene units, 2-pentene units, 1-hexene units, 2-hexene units, 3-hexene units, 1-heptene units, 1-octene units, 1-nonene units, 1-decene units, styrene units, vinyl chloride units, vinyl fluoride units, cyclopentene units, cyclohexene units, cycloheptene units, cyclooctene units, cyclononane units, cyclodecene units, cycloundecene units, cyclododecene, and norbornene units. In embodiments, the substance includes one or more co-polymers including one or more monomer units selected from ethylene units, propene units, 1-butene units, 2-butene units, isobutene units, 1-pentene units, 2-pentene units, 1-hexene units, 2-hexene units, 3-hexene units, 1-heptene units, 1-octene units, 1-nonene units, 1-decene units, styrene units, and vinyl chloride units. In embodiments, the substance includes one or more co-polymers including one or more monomer units selected from ethylene units, propene units, styrene units, and vinyl chloride units. In embodiments, the substance includes one or more co-polymers including one or more monomer units selected from ethylene units and propene units. In embodiments, the substance includes one or more co-polymers including one or more monomer units selected from ethylene units.

[0106] In embodiments, the substance includes one or more block co-polymers including one or more blocks selected from polyethylene block(s), polypropylene block(s), poly(vinyl chloride) block(s), polybutene block(s), polyisobutene block(s), poly(1-butene) block(s), poly(2-butene) block(s), polypentene block(s), poly(4-methyl-1-pentene) block(s), polystyrene block(s), poly(cyclopentene) block(s), poly(cyclohexene) block(s), poly(cycloheptene) block(s), poly(cyclooctene) block(s), poly(cyclononene) block(s), poly(cyclodecene) block(s), poly(cycloundecene) block(s), poly(cyclododecene) block(s), and polynorbornene. In embodiments, the substance includes one or more block co-polymers including one or more blocks selected from polyethylene block(s), polypropylene block(s), poly(vinyl chloride) block(s), polyisobutene block(s), poly(4-methyl-1-pentene) block(s), polystyrene block(s), and poly(cyclooctene) block(s). In embodiments, the substance includes one or more block co- polymers including one or more blocks selected from polyethylene block(s), polypropylene block(s), poly(vinyl chloride) block(s), and polystyrene block(s). In embodiments, the substance includes one or more block co-polymers including one or more blocks selected frompolyethylene block(s) and polypropylene block(s). In embodiments, the substance includes one or more block co-polymers including one or more blocks selected from polyethylene block(s).

[0107] In embodiments, the substance includes one or more homopolymers selected from polyethylene, polypropylene, polystyrene, poly(vinyl chloride), polybutene, polyisobutene, polybutene, poly(1-butene), poly(2-butene), polyisobutylene, polypentene, poly(4-methyl-1- pentene), polystyrene, and poly(vinyl chloride). In embodiments, the substance includes polyethylene. In embodiments, the substance is polyethylene. In embodiments, the substance includes waste polyethylene. In embodiments, the substance includes one or more polyethylenes. In embodiments, the substance is one or more polyethylenes. In embodiments, the substance includes one or more polyethylene(s) selected from high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and co-polymers thereof. In embodiments, the substance includes one or more polyethylene(s) selected from high-density polyethylene, low-density polyethylene, and co-polymers thereof. In embodiments, the substance includes one or more polyethylene(s) selected from high-density polyethylene and low-density polyethylene. In embodiments, the substance includes high-density polyethylene. In embodiments, the substance includes low-density polyethylene. In embodiments, the substance includes linear low-density polyethylene. In embodiments, the substance is high- density polyethylene. In embodiments, the substance is low-density polyethylene. In embodiments, the substance is linear low-density polyethylene.

[0108] In embodiments, the substance includes polypropylene. In embodiments, the substance includes syndiotactic polypropylene. In embodiments, the substance includes atactic polypropylene. In embodiments, the substance includes isotactic polypropylene.

[0109] In embodiments, the substance includes plastic waste. In embodiments, the substance includes plastic waste selected from milk jugs, shampoo bottles, lawn chairs, food containers, trash bags, barrels, drainage pipes, grocery bags, and cereal box liners.

[0110] In embodiments, the formation of one or more olefin units in the substance includes subjecting the substance to conditions for dehydrogenation. In embodiments, the formation of one or more olefin units in the substance includes conducting on the substance one or more dehydrogenation reactions. In embodiments, the one or more dehydrogenation reactions include one or more reactions including removal of one or more proton-hydride pairs, wherein each ofthe one or more proton-hydride pairs includes one proton and one hydride. In embodiments, the one or more dehydrogenation reactions transform a reactant into a dehydrogenated substance. In embodiments, the one or more dehydrogenation reactions include one or more acceptorless dehydrogenation reactions. In embodiments, the one or more dehydrogenation reactions include one or more transfer dehydrogenation reactions. In embodiments, the one or more dehydrogenation reactions include one or more transfer dehydrogenation reactions that include treatment of the substance with one or more hydrogen acceptors. In embodiments, the one or more dehydrogenation reactions include one or more oxidative dehydrogenation reactions. In embodiments, the one or more dehydrogenation reactions include treatment of the substance with one or more hydrogen acceptors. In embodiments, the one or more dehydrogenation reactions produce a dehydrogenated substance. In embodiments, the dehydrogenated substance is purified. In embodiments, the dehydrogenated substance is purified via one or more techniques selected from distillation or precipitation from one or more organic solvents, or precipitation from water.

[0111] In embodiments, the one one or more transfer dehydrogenation reactions include treatment with one or more hydrogen acceptor(s) including: one or more bonds independently selected from C-C bonds(s), C=C bond(s), C≡C bond(s), N-N bond(s), N=N bond(s), N≡N bond(s), O-O bond(s), O=O bond(s), C-N bond(s), C=N bond(s), C≡N bond(s), C-O bond(s), C=O bond(s), C≡O bond(s), S-S bond(s), C-S bond(s), and C=S bond(s); or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from C=C bond(s), C≡C bond(s), N=N bond(s), N≡N bond(s), O-O bond(s), O=O bond(s), C=N bond(s), C≡N bond(s), C=O bond(s), C≡O bond(s), S-S bond(s), and C=S bond(s); or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from C=C bond(s), C≡C bond(s), N=N bond(s), N≡N bond(s), O- O bond(s), O=O bond(s), C=N bond(s), C=O bond(s), C≡O bond(s), S-S bond(s), and C=S bond(s); or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from C=C bond(s), C≡C bond(s), N=N bond(s), O-O bond(s), O=O bond(s), C=N bond(s), C=O bond(s), C≡O bond(s), S-S bond(s), and C=S bond(s); or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from C=C bond(s), C≡C bond(s), N=N bond(s), O-O bond(s), O=O bond(s), C=O bond(s), and C≡O bond(s); or one or more rings. In embodiments, the one or more h drogen acceptors include: one or more bonds independently selected from C=C bond(s),C≡C bond(s), O-O bond(s), O=O bond(s), C=O bond(s), and C≡O bond(s); or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from C=C bond(s), C≡C bond(s), O=O bond(s), C=O bond(s), and C≡O bond(s); or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from C=C bond(s), C≡C bond(s), C=O bond(s), and C≡O bond(s); or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from C=C bond(s) and C≡C bond(s); or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from C=C bond(s) and C≡C bond(s). In embodiments, the one or more hydrogen acceptors include one or more C=C bond(s).

[0112] In embodiments, the one or more transfer dehydrogenation reactions include treatment with one or more hydrogen acceptors selected from ethylene, propylene, butene, tert- butylethylene, norbornene, norbornadiene, butadiene, styrene, acetylene, O2, CO2, CO, optionally substituted benzoquinone, and N2. In embodiments, the one or more hydrogen acceptors is indepdently selected from ethylene, propylene, butene, tert-butylethylene, norbornene, norbornadiene, butadiene, and styrene. In embodiments, the one or more hydrogen acceptors is independently selected from ethylene, propylene, tert-butylethylene, norbornene, and norbornadiene. In embodiments, the one or more hydrogen acceptors is independently selected from ethylene, propylene, tert-butylethylene, and norbornene. In embodiments, the one or more hydrogen acceptors is independently selected from ethylene, tert-butylethylene, and norbornene. In embodiments, the one or more hydrogen acceptors is independently selected from tert-butylethylene, and norbornene. In embodiments, the one or more hydrogen acceptors is independently selected from tert-butylethylene and norbornene. In embodiments, the one or more hydrogen acceptors is independently selected from norbornene. In embodiments, the one or more hydrogen acceptors is independently selected from tert-butylethylene. In embodiments, the one or more hydrogen acceptors is ethylene. In embodiments, the one or more hydrogen acceptors is propene.

[0113] In embodiments, the conditions for dehydrogenation include conducting one or more reactions at temperatures ranging from 20 to 1000 °C. In embodiments, the conditions for dehydrogenation include conducting one or more reactions at temperatures ranging from 50 to500 °C. In embodiments, the conditions for dehydrogenation include conducting one or more reactions at temperatures ranging from 100 to 400 °C. In embodiments, the conditions for dehydrogenation include conducting one or more reactions at temperatures ranging from 100 to 300 °C. In embodiments, the conditions for dehydrogenation include conducting one or more reactions at temperatures ranging from 100 to 200 °C. In embodiments, the dehydrogenation is conducted at a temperature of at least 20 °C, at least 50 °C, at least 65 °C, at least 80 °C, at least 100 ° C, at least 120 °C, at least 200 °C, at least 250 °C, at least 300 °C, at least 350 °C, at least 400 °C, at least 500 °C, at least 600 °C, at least 1000 °C, or more. Alternatively, or in addition, in embodiments, the dehydrogenation is conducted at a temperature of at most 20 °C, at most 50 °C, at most 65 °C, at most 80 °C, at most 100 ° C, at most 120 °C, at most 200 °C, at most 250 °C, at most 300 °C, at most 350 °C, at most 400 °C, at most 500 °C, at most 600 °C, at most 1000 °C, or less.

[0114] In embodiments, the conditions for dehydrogenation include conducting one or more reactions at a temperature of about 20 °C to about 1000 °C. In embodiments, the conditions for dehydrogenation include conducting one or more reactions at a temperature of at least about 20 °C. In embodiments, the conditions for dehydrogenation include conducting one or more reactions at a temperature of at most about 1000 °C. In embodiments, the conditions for dehydrogenation include conducting one or more reactions at a temperature of about 20 °C to about 65 °C, about 20 °C to about 100 °C, about 20 °C to about 150 °C, about 20 °C to about 200 °C, about 20 °C to about 300 °C, about 20 °C to about 350 °C, about 20 °C to about 400 °C, about 20 °C to about 450 °C, about 20 °C to about 500 °C, about 20 °C to about 600 °C, about 20 °C to about 1000 °C, about 65 °C to about 100 °C, about 65 °C to about 150 °C, about 65 °C to about 200 °C, about 65 °C to about 300 °C, about 65 °C to about 350 °C, about 65 °C to about 400 °C, about 65 °C to about 450 °C, about 65 °C to about 500 °C, about 65 °C to about 600 °C, about 65 °C to about 1000 °C, about 100 °C to about 150 °C, about 100 °C to about 200 °C, about 100 °C to about 300 °C, about 100 °C to about 350 °C, about 100 °C to about 400 °C, about 100 °C to about 450 °C, about 100 °C to about 500 °C, about 100 °C to about 600 °C, about 100 °C to about 1,000 °C, about 150 °C to about 200 °C, about 150 °C to about 300 °C, about 150 °C to about 350 °C, about 150 °C to about 400 °C, about 150 °C to about 450 °C, about 150 °C to about 500 °C, about 150 °C to about 600 °C, about 150 °C to about 1,000 °C, about 200 °C to about 300 °C, about 200 °C to about 350 °C, about 200 °C to about 400 °C,about 200 °C to about 450 °C, about 200 °C to about 500 °C, about 200 °C to about 600 °C, about 200 °C to about 1,000 °C, about 300 °C to about 350 °C, about 300 °C to about 400 °C, about 300 °C to about 450 °C, about 300 °C to about 500 °C, about 300 °C to about 600 °C, about 300 °C to about 1000 °C, about 350 °C to about 400 °C, about 350 °C to about 450 °C, about 350 °C to about 500 °C, about 350 °C to about 600 °C, about 350 °C to about 1,000 °C, about 400 °C to about 450 °C, about 400 °C to about 500 °C, about 400 °C to about 600 °C, about 400 °C to about 1000 °C, about 450 °C to about 500 °C, about 450 °C to about 600 °C, about 450 °C to about 1000 °C, about 500 °C to about 600 °C, about 500 °C to about 1000 °C, or about 600 °C to about 1000 °C. In embodiments, the conditions for dehydrogenation include conducting one or more reactions at a temperature of about 20 °C, about 65 °C, about 100 °C, about 150 °C, about 200 °C, about 300 °C, about 350 °C, about 400 °C, about 450 °C, about 500 °C, about 600 °C, or about 1000 °C.

[0115] In embodiments, the conditions for dehydrogenation include subjecting a neat substance to one or more dehydrogenation reaction(s). In embodiments, the conditions for dehydrogenation include melting the substance. In embodiments, the conditions for dehydrogenation include melting the polymer. In embodiments, the conditions for dehydrogenation include melting the polyethylene.

[0116] In embodiments, the conditions for dehydrogenation include contacting a substance with one or more solvents. In embodiments, the conditions for dehydrogenation include contacting a substance with one or more organic solvents. In embodiments, the conditions for dehydrogenation include contacting a substance with one or more hydrocarbon solvents. In embodiments, the conditions for dehydrogenation include contacting a substance with one or more solvents selected from benzene, toluene, o-xylene, m-xylene, p-xylene, dichlorobenzene (e.g., o-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), dioxane, tetrahydrofuran, tetrahydropyran, acetone, chloroform, carbon tetrachloride, dichloromethane, ethyl acetate, pentane, pentanes, hexane, hexanes, heptane, heptanes, octane, octanes, nonane, nonanes, decane, decanes, undecane, undecanes, dodecane, and dodecanes. In embodiments, the conditions for dehydrogenation include contacting a substance with a mixture of multiple organic solvents.

[0117] In embodiments, the conditions for dehydrogenation include conducting a batch reaction. In embodiments, the conditions for dehydrogenation include flowing one or more gases over the headspace of a batch reaction. In embodiments, the conditions for dehydrogenation include flowing one or more gases selected from helium, argon, nitrogen, and hydrogen over the headspace of a batch reaction.

[0118] In embodiments, the conditions for dehydrogenation include contacting a substance with one or more dehydrogenation catalysts. In embodiments, the one or more dehydrogenation catalysts includes a homogeneous catalyst. In embodiments, the one or more dehydrogenation catalysts includes a heterogeneous catalyst. In embodiments, the one or more dehydrogenation catalysts is (are) immobilized.

[0119] In embodiments, the formation of one or more olefin units in the substance includes subjecting the substance to conditions for cracking. In embodiments, the (i) conducting one or more reaction(s) to form one or more olefin units in the substance includes subjecting the substance to conditions for cracking. In embodiments, the cracking is thermal cracking. In embodiments, the cracking is catalytic cracking. In embodiments, the cracking is fluid catalytic cracking. In embodiments, the cracking includes hydrocracking. In embodiments, the conditions for cracking include heating to a temperature of 100 °C to 900 °C. In embodiments, the conditions for cracking include heating to a temperature of 300 °C to 700 °C. In embodiments, the conditions for cracking include heating to a temperature of 300 °C to 600 °C. In embodiments, the conditions for cracking include heating to a temperature of 400 °C to 650 °C. In embodiments, the conditions for cracking include treatment with one or more catalysts selected from alumina, silica, zeolite X, and zeolite Y. In embodiments, the conditions for cracking include selectively forming olefins from paraffins. In embodiments, the conditions for cracking include selectively forming monoenes or nonconjugated dienes from paraffins. In embodiments, the conditions for cracking include selectively forming monoenes from paraffins.

[0120] In embodiments, the formation of one or more olefin units includes a polymerization. In embodiments, the polymerization includes termination of chain growth. In embodiments, the polymerization includes termination of chain growth to release one or more olefin units. In embodiments, the termination of chain growth includes β-hydride elimination. In embodiments, the termination of chain growth includes chain-transfer to monomer. In embodiments, theformation of one or more olefin units includes a polymerization of one or more monomer units or co-monomer units including two or more degrees of unsaturation. In embodiments, the one or more monomer units co-monomer units including two or more degrees of unsaturation is a polyene (e.g., diene) or alkyne. In embodiments, the one or more monomer units co-monomer units including two or more degrees of unsaturation is selected from butadiene, acetylene, and norbornadiene.

[0121] In embodiments, the formation of one or more olefin units includes post-polymerization modification. In embodiments, the the post-polymerization modification includes one or more reaction sequences selected from (i) C-H olefination; (ii) C-H functionalization to install a heteroatom, X, followed by elimination of HX; (iii) CH formylation to install an aldehyde followed by Wittig coupling; (iv) CH carboxylation to install an ester followed by treatment with Tebbe’s reagent or Petasis reagent; (v) Julia olefination; and (vi) CH alkynylation to install one or more alkynes followed by reduction of the one or more alkynes to alkenes. In embodiments, the post-polymerization modification includes C-H functionalization to install a heteroatom, X, followed by elimination of HX. In embodiments, the post-polymerization modification includes C-H halogenation, followed by elimination. In embodiments, the post-polymerization modification includes C-H halogenation, followed by base-promoted elimination.

[0122] In embodiments, the formation of one or more olefin units includes installation of a leaving group on a substance. In embodiments, the formation of one or more olefin units includes installation of a leaving group on a substance and elimination of the leaving group. In embodiments, the leaving group is selected from -F, -Cl, -Br, -I, -OTf, -OTs, -OMs, -(OR2)+, - (NR3)+, OC(O)R, OC(O)OR, OC(O)X, and SO2R, wherein R and X are independently selected from H, substituted or unsubstituted C1-C30alkyl, and 3 to 10 membered heterocycloalkyl. In embodiments, the leaving group is selected from -F, -Cl, -Br, and -I. In embodiments, the leaving group is selected from -Cl, -Br, and -I. In embodiments, the leaving group is -I.

[0123] In embodiments, the method further includes a pre-metathesis step conducted after the (i) forming one or more olefins, before the (ii) subjecting to conditions for olefin metathesis, and before the (iii) subjecting to conditions for olefin isomerization. In embodiments, the pre- metathesis step includes treating with one or more olefin metathesis catalysts. In embodiments, the pre-metathesis step includes treating with one or more olefins. In embodiments, the pre-metathesis step includes treating with ethylene. In embodiments, the pre-metathesis step includes treating with ethylene and one or more olefin metathesis catalysts.

[0124] In embodiments, the conditions for olefin metathesis include treatment with one or more olefins. In embodiments, the conditions for olefin metathesis include treatment with one or more exogenously added olefins. In embodiments, the conditions for olefin metathesis include treatment with 0.1-1000 equiv of the one or more olefins. In embodiments, the conditions for olefin metathesis include treatment with one or more olefins independently selected from C2-C40olefins. In embodiments, the conditions for olefin metathesis include treatment with an optionally substituted C2 olefin. In embodiments, the conditions for olefin metathesis include treatment with one or more olefins independently selected from ethylene, propylene, 1-butene, 2- butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-hepene, 1- octene, 2-octene, 3-octene, 4-octene, 1-nonene, 2-nonene, 3-nonene, 4-nonene, 1-decene, 2- decene, 3-decene, 4-decene, 5-decene, 1-undecene, 2-undecene, 3-undecene, 4-undecene, 5- undecene, 1-dodecene, 2-dodecene, 3-dodecene, 4-dodecene, 5-dodecene, 6-dodecene, 1- tridecene, 2-tridecene, 3-tridecene, 4-tridecene, 5-tridecene, 6-tridecene, 1-tetradecene, 2- tetradecene, 3-tetradecene, 4-tetradecene, 5-tetradecene, 6-tetradecene, and 7-tetradecene.

[0125] In embodiments, the one or more olefins include one or more gaseous olefins. In embodiments, the conditions for olefin metathesis include treatment with 0.1-1000 bar of the one or more gaseous olefins. In embodiments, the conditions for olefin metathesis include treatment with 5-100 bar of the one or more gaseous olefins. In embodiments, the conditions for olefin metathesis include treatment with 10-100 bar of the one or more gaseous olefins. In embodiments, the conditions for olefin metathesis include treatment with ethylene. In embodiments, the conditions for olefin metathesis include treatment with ethylene in a pressure of 0.1-1000 bar. In embodiments, the conditions for olefin metathesis include conditions for ethenolysis. In embodiments, the conditions for olefin metathesis include treatment with propylene. In embodiments, the conditions for olefin metathesis include treatment with propylene in a pressure of 0.1-1000 bar. In embodiments, the conditions for olefin metathesis include conditions for propenolysis. In embodiments, the conditions for olefin metathesis include treatment with butenes. In embodiments, the conditions for olefin metathesis include treatment with butenes in a pressure of 0.1-1000 bar. In embodiments, the conditions for olefinmetathesis include conditions for butenolysis. In embodiments, the conditions for olefin metathesis include treatment with 2-butene. In embodiments, the conditions for olefin metathesis include treatment with 2-butene in a pressure of 0.1-1000 bar. In embodiments, the conditions for olefin metathesis include conditions for 2-butenolysis. In embodiments, the conditions for olefin metathesis include treatment with ethylene and one or more olefin metathesis catalysts.

[0126] In embodiments, the conditions for olefin metathesis include heating at 20-500 °C. In embodiments, the conditions for olefin metathesis include heating at 20-200 °C. In embodiments, the conditions for olefin metathesis include heating at 40-170 °C. In embodiments, the conditions for olefin metathesis include heating at 40-160 °C. In embodiments, the conditions for olefin metathesis include heating at 140-170 °C. In embodiments, the conditions for olefin metathesis include heating at 40-100 °C.

[0127] In embodiments, a neat substance is subjected to the conditions for olefin metathesis. In embodiments, the conditions for olefin metathesis include melting the dehydrogenated substance. In embodiments, the conditions for olefin metathesis include melting a polymer. In embodiments, the conditions for olefin metathesis include contacting a substance with one or more solvents. In embodiments, the conditions for olefin metathesis include contacting a substance with one or more organic solvents. In embodiments, the conditions for olefin metathesis include contacting a substance with one or more hydrocarbon solvents. In embodimetns, the conditions for olefin metathesis include contacting a substance with one or more solvents selected from benzene, toluene, o-xylene, m-xylene, p-xylene, dichlorobenzene (e.g., o-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), dioxane, tetrahydrofuran, tetrahydropyran, acetone, chloroform, carbon tetrachloride, dichloromethane, ethyl acetate, pentane, pentanes, hexane, hexanes, heptane, heptanes, octane, octanes, nonane, nonanes, decane, decanes, undecane, undecanes, dodecane, and dodecanes.

[0128] In embodiments, the conditions for olefin metathesis include conducting a batch reaction. In embodiments, the conditions for olefin metathesis include flowing one or more gases over the headspace of a batch reaction. In embodiments, the conditions for olefin metathesis include conducting a continuous-flow reaction. In embodiments, the conditions forolefin metathesis include flowing one or more gases selected from helium, argon, nitrogen, and hydrogen over the headspace of a batch reaction.

[0129] In embodiments, the conditions for olefin metathesis include contacting the substance with one or more olefin metathesis catalysts. In embodiments, the one or more olefin metathesis catalysts include one or more homogeneous catalyst(s). In embodiments, the one or more olefin metathesis catalysts include one or more heterogeneous catalyst(s). In embodiments, one or more of the one or more olefin metathesis catalysts is (are) immobilized. In embodiments, the one or more olefin metathesis catalyst(s) is / are selected from Schrock-type olefin metathesis catalyst(s), Grubbs-type olefin metathesis catalyst(s), Hoveyda / Grubbs-type olefin metathesis catalyst(s), and heterogenous-type olefin metathesis catalyst(s). In embodiments, the one or more olefin metathesis catalysts includes Hoveyda Grubbs II. In embodiments, the one or more olefin metathesis catalysts is Hoveyda Grubbs II. In embodiments, the one or more olefin metathesis catalysts includes Ultra-Nitro-Cat. In embodiments, the one or more olefin metathesis catalysts includes Re2O7. In embodiments, the one or more olefin metathesis catalysts includes Re2O7 on alumina. In embodiments, the one or more olefin metathesis catalysts includes Re2O7on silica. In embodiments, the one or more olefin metathesis catalysts includes Re2O7on a zeolite. In embodiments, the one or more olefin metathesis catalysts includes Re2O7 on zeolite Y. In embodiments, the one or more olefin metathesis catalysts includes tungsten.

[0130] In embodiments, the conditions for olefin metathesis include conducting more than one metathesis reaction conducted per molecule present in the substance. In embodimetns, the conditions for olefin metathesis include conducting more than one nondegenerate metathesis reaction conducted per molecule present in the substance. In embodiments, the conditions for olefin metathesis include conducting 2-100,000 nondegenerate metathesis reactions per molecule present in the substance.

[0131] In embodiments, the conditions for olefin isomerization include conditions for positional olefin isomerization. In embodiments, the conditions for olefin isomerization include conditions for positional, long-range olefin isomerization. In embodiments, the conditions for olefin isomerization include conditions for positional, short-range olefin isomerization. In embodiments, the conditions for olefin isomerization include conditions for isomerization ofterminal olefins to internal olefins. In embodiments, the conditions for olefin isomerization include conducting one or more olefin isomerization(s) proceeding through one or more intermediate(s) independently selected from metal-hydride intermediate(s), metal-allyl intermediate(s), cationic intermediate(s), carbocationic intermediate(s), anionic intermediate(s), carbanionic intermediate(s), radical intermediate(s), metal-radical intermediate(s), radical cationic intermediate(s), and radical anionic intermediate(s). In embodiments, the one or more olefin isomerization(s) proceed(s) through one or more metal-hydride intermediate(s). In embodiments, the one or more olefin isomerization(s) proceed(s) through one or more metal- allyl intermediate(s). In embodiments, the one or more olefin isomerization(s) proceed(s) through one or more cationic intermediate(s).

[0132] In embodiments, the conditions for olefin isomerization include heating at 20 °C to 1000 °C. In embodiments, the conditions for olefin isomerization include heating at 20 °C to 200 °C. In embodiments, the conditions for olefin isomerization include heating at 20 °C to 175 °C.

[0133] In embodiments, a neat substance is subjected to the conditions for olefin isomerization. In embodiments, the conditions for olefin isomerization include melting the dehydrogenated substance. In embodiments, the conditions for olefin isomerization include melting the polymer. In embodiments, the conditions for olefin isomerization include contacting a substance with one or more solvents. In embodiments, the conditions for olefin isomerization include contacting a substance with one or more solvents selected from benzene, toluene, o- xylene, m-xylene, p-xylene, dichlorobenzene (e.g., o-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), dioxane, tetrahydrofuran, tetrahydropyran, acetone, chloroform, carbon tetrachloride, dichloromethane, ethyl acetate, pentane, pentanes, hexane, hexanes, heptane, heptanes, octane, octanes, nonane, nonanes, decane, decanes, undecane, undecanes, dodecane, and dodecanes. In embodiments, the conditions for olefin isomerization include treatment with one or more bases.

[0134] In embodiments, the conditions for olefin isomerization include contacting a substance with one or more olefin isomerization catalysts. In embodiments, the one or more olefin isomerization catalysts include a homogeneous catalyst. In embodiments, the one or more olefin isomerization catalysts include a heterogeneous catalyst. In embodiments, the one or more olefinisomerization catalysts include an immobilized catalyst. In embodiments, the conditions for olefin isomerization include treatment with one or more olefin isomerization catalysts. In embodiments, the conditions for olefin isomerization include treatment with one or more homogeneous olefin isomerization catalysts. In embodiments, the conditions for olefin isomerization include treatment with one or more heterogeneous olefin isomerization catalysts.

[0135] In embodiments, the conditions for olefin isomerization include conducting a batch reaction. In embodiments, the conditions for olefin isomerization include flowing one or more gases over the headspace of a batch reaction. In embodiments, the conditions for olefin isomerization include conducting a continuous-flow reaction. In embodiments, the conditions for olefin isomerization include flowing one or more gases selected from helium, argon, nitrogen, and hydrogen over the headspace of a batch reaction.

[0136] In embodiments, the (b) subjecting to conditions for olefin metathesis and the (c) subjecting to conditions for olefin isomerization are collectively conducted as an isomerizing olefin metathesis. In embodiments, the one or more olefins formed in the (a) forming one or more olefins is subjected to an isomerizing olefin metathesis. In embodiments, the isomerizing olefin metathesis includes an isomerizing ethenolysis. In embodiments, the isomerizing olefin metathesis is an isomerizing ethenolysis. In embodiments, the isomerizing olefin metathesis includes repetition of a cycle including (i) olefin metathesis and (ii) olefin isomerization. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1- 500,000 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1-200,000 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1-100,000 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1-50,000 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1- 5,000 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 500 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1-50 times. In embodients, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated at least 1 time, at least 50 times, at least 100 times, at least 500 times, at least 2000 times, at least 10,000 times, at least 50,000 times, at least 100,000 times, at least 500,000 or more. Alternatively, or in addition, in embodients, the cycleincluding (i) olefin metathesis and (ii) olefin isomerization is repeated at most 1 time, at most 50 times, at most 100 times, at most 500 times, at most 2000 times, at most 10,000 times, at most 50,000 times, at most 100,000 times, at most 500,000 or less.

[0137] In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated about 1 time to about 500,000 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated at least about 1 time. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated at most about 500,000 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated about 1 time to about 50 times, about 1 time to about 100 times, about 1 time to about 500 times, about 1 time to about 1,000 times, about 1 time to about 5,000 times, about 1 time to about 10,000 times, about 1 time to about 25,000 times, about 1 time to about 50,000 times, about 1 time to about 100,000 times, about 1 time to about 250,000 times, about 1 time to about 500,000 times, about 50 times to about 100 times, about 50 times to about 500 times, about 50 times to about 1,000 times, about 50 times to about 5,000 times, about 50 times to about 10,000 times, about 50 times to about 25,000 times, about 50 times to about 50,000 times, about 50 times to about 100,000 times, about 50 times to about 250,000 times, about 50 times to about 500,000 times, about 100 times to about 500 times, about 100 times to about 1,000 times, about 100 times to about 5,000 times, about 100 times to about 10,000 times, about 100 times to about 25,000 times, about 100 times to about 50,000 times, about 100 times to about 100,000 times, about 100 times to about 250,000 times, about 100 times to about 500,000 times, about 500 times to about 1,000 times, about 500 times to about 5,000 times, about 500 times to about 10,000 times, about 500 times to about 25,000 times, about 500 times to about 50,000 times, about 500 times to about 100,000 times, about 500 times to about 250,000 times, about 500 times to about 500,000 times, about 1,000 times to about 5,000 times, about 1,000 times to about 10,000 times, about 1,000 times to about 25,000 times, about 1,000 times to about 50,000 times, about 1,000 times to about 100,000 times, about 1,000 times to about 250,000 times, about 1,000 times to about 500,000 times, about 5,000 times to about 10,000 times, about 5,000 times to about 25,000 times, about 5,000 times to about 50,000 times, about 5,000 times to about 100,000 times, about 5,000 times to about 250,000 times, about 5,000 times to about 500,000 times, about 10,000 times to about 25,000 times, about 10,000 times to about 50,000 times, about 10,000 times to about 100,000 times, about 10,000 times to about 250,000 times,about 10,000 times to about 500,000 times, about 25,000 times to about 50,000 times, about 25,000 times to about 100,000 times, about 25,000 times to about 250,000 times, about 25,000 times to about 500,000 times, about 50,000 times to about 100,000 times, about 50,000 times to about 250,000 times, about 50,000 times to about 500,000 times, about 100,000 times to about 250,000 times, about 100,000 times to about 500,000 times, or about 250,000 times to about 500,000 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated about 1 time, about 50 times, about 100 times, about 500 times, about 1,000 times, about 5,000 times, about 10,000 times, about 25,000 times, about 50,000 times, about 100,000 times, about 250,000 times, or about 500,000 times.

[0138] In embodiments, the isomerizing olefin metathesis is conducted at 20-500 °C. In embodiments, a neat substance is subjected to the conditions for isomerizing olefin metathesis. In embodiments, the conditions for isomerizing olefin metathesis include melting the dehydrogenated substance. In embodiments, the conditions for isomerizing olefin metathesis include melting a polymer. In embodiments, the conditions for isomerizing olefin metathesis include contacting a substance with one or more solvents. In embodiments, the conditions for isomerizing olefin metathesis include contacting a substance with one or more solvents selected from benzene, toluene, o-xylene, m-xylene, p-xylene, dichlorobenzene (e.g., o-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), dioxane, tetrahydrofuran, tetrahydropyran, acetone, chloroform, carbon tetrachloride, dichloromethane, ethyl acetate, pentane, pentanes, hexane, hexanes, heptane, heptanes, octane, octanes, nonane, nonanes, decane, decanes, undecane, undecanes, dodecane, dodecanes. In embodiments, the conditions for isomerizing olefin metathesis include treatment with one or more bases.

[0139] In embodiments, the conditions for isomerizing olefin metathesis include contacting a substance with one or more olefin metathesis catalysts. In embodiments, one or more of the one or more olefin metathesis catalysts is capable of olefin isomerization. In embodiments, the conditions for isomerizing olefin metathesis include contacting a substance with one or more olefin isomerization catalysts. In embodiments, one or more of the one or more olefin isomerization catalysts is capable of catalyzing olefin metathesis. In embodiments, the conditions for isomerizing olefin metathesis include contacting a substance with one or more olefin metathesis catalysts and with one or more olefin isomerization catalysts.

[0140] In embodiments, the conditions for isomerizing olefin metathesis include conducting a batch reaction. In embodiments, the conditions for isomerizing olefin metathesis include flowing one or more gases over the headspace of a batch reaction. In embodiments, the conditions for isomerizing olefin metathesis include conducting a continuous-flow reaction. In embodiments, the conditions for isomerizing olefin metathesis include flowing one or more gases selected from helium, argon, nitrogen, and hydrogen over the headspace of a batch reaction. In embodiments, the conditions for isomerizing olefin metathesis include continuously removing one or more gases. In embodiments, the conditions for isomerizing olefin metathesis include continuously removing propene. In embodiments, the conditions for isomerizing olefin metathesis include continuously adding one or more gases. In embodiments, the conditions for isomerizing olefin metathesis include continuously adding ethylene.

[0141] In embodiments, the method produces olefins. In embodiments, the method produces olefins that include fewer carbons per molecule than the substance. In embodiments, the method further includes reactive distillation. In embodiments, the method produces propene. In embodiments, the method produces propene in a yield of 0.1 to 100%. In embodiments, the method produces propene in a yield of 50% to 100%. In embodiments, the method produces propene in a yield of 50% to 99.9%. In embodiments, the method produces propene in a yield of 50% to 99%. In embodiments, the method produces propene in a yield of 60% to 95%. In embodiments, the method produces propene in a selectivity of 0% to 100%. In embodiments, the method produces propene in a selectivity of 0.01% to 99.99%. In embodiments, the method produces propene in a selectivity of 1% to 99.99%. In embodiments, the method produces propene in a selectivity of 50% to 99.99%.

[0142] In an aspect is provided a method of making an alkene, the method including mixing a dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s); wherein: (i) the dehydrogenated polymer includes at least 20 carbon atoms; or (ii) prior to the mixing, the method includes mixing a polymer with one or more dehydrogenating reagent(s), thereby forming the dehydrogenated polymer.

[0143] In an aspect is provided a method of making an alkene, the method including mixing a dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s); wherein: (i) the dehydrogenated polymer includes at most 10%unsaturated alkene monomer units; (ii) the dehydrogenated polymer includes at least 20 carbon atoms; or (iii) prior to the mixing, the method includes mixing a polymer with one or more dehydrogenating reagent(s), thereby forming the dehydrogenated polymer.

[0144] In an aspect is provided a method of making a dehydrogenated polymer, the method including mixing a polymer with one or more dehydrogenating reagent(s), wherein: (i) a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units in the dehydrogenated polymer are unsaturated; (ii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da or greater; (iii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da and a percentage of 0.01% to 10% of monomer units are unsaturated; or (iv) the dehydrogenated polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da and a percentage of from 0.01% to from 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated.

[0145] In embodiments, the substituted or unsubstituted alkene is a substituted or unsubstituted propene. In embodiments, the first substance is a substituted or unsubstituted dehydrogenated polyethylene.

[0146] In embodiments, the the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 6,500 Da or from about 6,700 Da to about 15,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 6,500 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 6,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 5,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 4,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 4,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 500,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 400,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 300,000 Da. In embodiments, the dehydrogenated polymer has anumber average molecular weight of from about 6,700 Da to about 200,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 100,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 80,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 60,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 40,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 20,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 15,000 Da.

[0147] In embodiments, the the dehydrogenated polymer has a number average molecular weight of from 2,200 Da to 6,500 Da or from 6,700 Da to 15,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 2,200 Da to 6,500 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 2,200 Da to 6,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 2,200 Da to 5,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 2,200 Da to 4,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 2,200 Da to 4,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 500,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 400,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 300,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 200,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 100,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 80,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 60,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 40,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 20,000 Da. In embodiments, thedehydrogenated polymer has a number average molecular weight of from 6,700 Da to 15,000 Da.

[0148] In embodiments, a percentage of from about 10% or less of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 0.01% to about 11% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 0.01% to about 10% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 0.01% to about 9% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 0.01% to about 8% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 0.01% to about 1.5% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 2.4% to about 4.3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 4.5% to about 13.2% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 1% to about 3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 1.5% to about 3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 1.7% to about 2.3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 1.7% to about 2.1% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 1.9% to about 2.1% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of about 1.7% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of about 1.8% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of about 1.9% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of about 2% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of about 2.1% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of about 2.2% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of about 2.3% of monomer units in the dehydrogenated polymer are unsaturated.

[0149] In embodiments, a percentage of 10% or less of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 0.01% to 11% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 0.01% to 10% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 0.01% to 9% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 0.01% to 8% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 0.01% to 1.5% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 2.4% to 4.3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 4.5% to 13.2% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 1% to 3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 1.5% to 3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 1.7% to 2.3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 1.7% to 2.1% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 1.9% to 2.1% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of 1.7% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of 1.8% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of 1.9% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of 2% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of 2.1% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of 2.2% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of 2.3% of monomer units in the dehydrogenated polymer are unsaturated.

[0150] In embodiments, the dehydrogenated polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 100,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in thedehydrogenated polymer are unsaturated. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 50,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 20,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 10,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated.

[0151] In embodiments, the method further includes mixing the dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s), thereby forming an alkene.

[0152] In embodiments, the dehydrogenated polymer is a substituted or unsubstituted dehydrogenated polyethylene. In embodiments, the alkene is a substituted or unsubstituted propene.

[0153] In embodiments, the dehydrogenated polymer, the one or more olefin metathesis reagent(s), and the one or more isomerization reagent(s) are mixed simultaneously. In embodiments, the dehydrogenated polymer and the one or more olefin metathesis reagent(s) are mixed prior to adding the one or more isomerization reagent(s). In embodiments, the dehydrogenated polymer and one or more additional olefin metathesis reagent(s) are mixed prior to adding the one or more olefin metathesis reagent(s) and the one or more isomerization reagent(s).

[0154] In embodiments, the one or more olefin metathesis reagent(s) includes an ethenolysis catalyst. In embodiments, the one or more olefin metathesis reagent(s) includes one or more homogeneous olefin metathesis catalyst(s) or one or more heterogeneous olefin metathesiscatalyst(s). In embodiments, the one or more olefin metathesis reagent(s) includes one or more homogeneous olefin metathesis catalyst(s). In embodiments, the one or more olefin metathesis reagent(s) includes one or more heterogeneous olefin metathesis catalyst(s). In embodiments, the one or more olefin metathesis reagent(s) further includes ethylene.

[0155] In embodiments, the homogeneous olefin metathesis catalyst isembodiments, the homogeneous olefin metathesis catalystembodiments, the homogeneous olefin metathesis catalyst iembodiments, the homogeneous olefin metathesis catalysthomogeneous olefin metathesis catalyst.

[0156] In embodiments, the heterogeneous olefin metathesis catalyst is Re2O7 / Al2O3 or WO3 / Al2O3. In embodiments, the heterogeneous olefin metathesis catalyst is Re2O7 / Al2O3. In embodiments, the heterogeneous olefin metathesis catalyst is WO3 / Al2O3.

[0157] In embodiments, the one or more isomerization reagent(s) includes one or more homogeneous isomerization catalyst(s) or one or more heterogeneous isomerization catalyst(s). In embodiments, the one or more isomerization reagent(s) includes one or more homogeneous isomerization catalyst(s). In embodiments, the one or more isomerization reagent(s) includes one or more heterogeneous isomerization catalyst(s).

[0158] In embodiments, the one or more homogeneous isomerization catalyst(s) is selected from:. In embodiments, the one or more homogeneous isomerization catalyst(s) is . In embodiments, the one or omogeneous isomerization catalyst(s) isone or more homogeneous isomerization catalyst(s) is .embodiments, the one or more homogeneous isomerization catalyst(s) is .

[0159] In embodiments, the one or more heterogeneous isomerization catalyst(s) is selected from: Na / Al2O3, K / Al2O3, Mg / Al2O3, MgO, NaO2, and KO2. In embodiments, the one or more heterogeneous isomerization catalyst(s) is Na / Al2O3. In embodiments, the one or more heterogeneous isomerization catalyst(s) is K / Al2O3. In embodiments, the one or more heterogeneous isomerization catalyst(s) is Mg / Al2O3. In embodiments, the one or more heterogeneous isomerization catalyst(s) is MgO. In embodiments, the one or more heterogeneous isomerization catalyst(s) is NaO2. In embodiments, the one or more heterogeneous isomerization catalyst(s) is KO2.

[0160] In embodiments, the one or more heterogeneous isomerization catalyst includes a Group VI or Group VII metal (W, Mo, Re) on SiO2 or Al2O3. In embodiments, Group VI or Group VII metal (W, Mo, Re) on SiO2or Al2O3is first treated with a mild base (e.g., Na2CO3). Without being bound to any particulary theory, in embodiments the mild base is sufficient to neutralize acidic sites. In embodiments, the one or more heterogeneous isomerization catalyst includes K, Na, Na / K alloy, or Li supported on Al2O3. In embodiments, the one or more heterogeneous isomerization catalyst includes includes an alkali metal (e.g., a Group VI or Group VII metal such as W, Mo, Re) and a SiO2 support. In embodiments, the one or more heterogeneous isomerization catalyst includes K, Na, Na / K alloy, or Li supported on SiO2.

[0161] In embodiments, the one or more heterogeneous metathesis catalyst further includes a tin promoter. In embodiments, the tin promotor is a tetraalkyl tin promotor. In embodiments, the one or more heterogeneous metathesis catalyst further includes a tetramethyl tin promoter. In embodiments, the one or more metathesis isomerization catalyst further includes a tetraethyl tin promoter. In embodiments, the one or more heterogeneous metathesis catalyst further includes a tetrapropyl tin promoter. In embodiments, the one or more heterogeneous metathesis catalyst further includes a tetrabutyl tin promoter. In embodiments, the one or more heterogeneous metathesis catalyst further includes a tetrabenzyl tin promoter.

[0162] In embodiments, the substituted or unsubstituted polymer is a high-density polyethylene, a low-density polyethylene, or a linear low-density polyethylene, or a co-polymer thereof. In embodiments, the substituted or unsubstituted polymer is a high-density polyethylene. In embodiments, the substituted or unsubstituted polymer is a low-density polyethylene. In embodiments, the substituted or unsubstituted polymer is a linear low-density polyethylene.

[0163] In embodiments, the one or more dehydrogenating reagent(s) includes a transfer dehydrogenation catalyst.

[0164] In embodiments, the one or more dehydrogenating reagent(s) includes a hydrogen acceptor. In embodiments, the hydrogen acceptor includes a C-C bond, a C=C bond, a C≡C bond, an N-N bond, an N=N bond, an N≡N bond, an O-O bond, an O=O bond, a C-N bond, a C=N bond, a C≡N bond, a C-O bond, a C=O bond, a C≡O bond, an S-S bond, a C-S bond, or a C=S bond. In embodiments, the hydrogen acceptor includes a C-C bond. In embodiments, thehydrogen acceptor includes a C=C bond. In embodiments, the hydrogen acceptor includes a C≡C bond. In embodiments, the hydrogen acceptor includes an N-N bond. In embodiments, the hydrogen acceptor includes an N=N bond. In embodiments, the hydrogen acceptor includes an N≡N bond. In embodiments, the hydrogen acceptor includes an O-O bond. In embodiments, the hydrogen acceptor includes an O=O bond. In embodiments, the hydrogen acceptor includes a C- N bond. In embodiments, the hydrogen acceptor includes a C=N bond. In embodiments, the hydrogen acceptor includes a C≡N bond. In embodiments, the hydrogen acceptor includes a C-O bond. In embodiments, the hydrogen acceptor includes a C=O bond. In embodiments, the hydrogen acceptor includes a C≡O bond. In embodiments, the hydrogen acceptor includes an S- S bond. In embodiments, the hydrogen acceptor includes a C-S bond. In embodiments, the hydrogen acceptor includes a C=S bond.

[0165] In embodiments, the hydrogen acceptor is ethylene, propylene, butene, tert- butylethylene, norbornene, norbornadiene, butadiene, styrene, acetylene, O2, CO2, CO, substituted or unsubstituted benzoquinone, or N2. In embodiments, the hydrogen acceptor is ethylene. In embodiments, the hydrogen acceptor is propylene. In embodiments, the hydrogen acceptor is butane. In embodiments, the hydrogen acceptor is tert-butylethylene. In embodiments, the hydrogen acceptor is norbornene. In embodiments, the hydrogen acceptor is norbornadiene. In embodiments, the hydrogen acceptor is butadiene. In embodiments, the hydrogen acceptor is styrene. In embodiments, the hydrogen acceptor is acetylene. In embodiments, the hydrogen acceptor is O2. In embodiments, the hydrogen acceptor is CO2. In embodiments, the hydrogen acceptor is CO. In embodiments, the hydrogen acceptor is substituted or unsubstituted benzoquinone. In embodiments, the hydrogen acceptor is N2.

[0166] In embodiments, the one or more dehydrogenating reagent(s) includes a heterogeneous dehydrogenating catalyst. In embodiments, the heterogeneous dehydrogenating catalyst includes a plurality of metallic elements. In embodiments, the heterogeneous dehydrogenating catalyst is a bimetallic catalyst. In embodiments, the heterogeneous dehydrogenating catalyst is a Pt / Sn catalyst or a Pt / Zn catalyst. In embodiments, the heterogeneous dehydrogenating catalyst is a Pt / Sn catalyst. In embodiments, the heterogeneous dehydrogenating catalyst is a Pt / Zn catalyst. In embodiments, the heterogeneous dehydrogenating catalyst is Pt / Sn-Al2O3. In embodiments, the heterogeneous dehydrogenating catalyst is Pt / Zn-SiO2.

[0167] In embodiments, the one or more dehydrogenating reagent(s) includes a homogeneous dehydrogenating catalyst. In embodiments, the homogeneous dehydrogenating catalyst includes an iridium catalyst. In embodiments, the homogeneous dehydrogenating catalyst includes a rhodium catalyst. In embodiments, the homogeneous dehydrogenating catalyst includes a ruthenium catalyst.

[0168] In embodiments, the one or more dehydrogenating reagent(s) includes (R)-(−)-5,5′- Bis[di(3,5-di-tert-butyl-4-methoxyphenyl)phosphino]-4,4′-bi-1,3-benzodioxole, [(4R)-(4,4′-bi- 1,3-benzodioxole)-5,5′-diyl]bis[bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphine], also commonly referred to as (R)-DTBM-SEGPHOS. In embodiments, the one or more dehydrogenating reagent(s) includes (R)-(−)-5,5′-Bis[di(3,5-di-tert-butyl-4- methoxyphenyl)phosphino]-4,4′-bi-1,3-benzodioxole, [(4R)-(4,4′-bi-1,3-benzodioxole)-5,5′- diyl]bis[bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphine] and an iridium catalyst.

[0169] In embodiments, the homogeneous dehydrogenating catalyst has the formula:.

[0170] M is Ir, Rh, Ru, or Os.

[0171] L1and L2are independently –O-, -S-, -NR6-, or substituted or unsubstituted alkylene (e.g., C1-C8, C1-C6, C1-C4, or C1-C2).

[0172] Each R3and R4is independently substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, or 2 to 3 membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted or unsubstituted aryl (e.g., C6-C10or phenyl), or substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered).

[0173] R5is independently halogen, -CX53, -CHX52, -CH2X5, -OCX53, -OCH2X5, -OCHX52, -CN, -SOn5R5D, -SOv5NR5AR5B, ^NR5CNR5AR5B, ^ONR5AR5B, -NR5CC(O)NR5AR5B, -N(O)m5, -NR5AR5B, -C(O)R5C, -C(O)OR5C, -OC(O)R5C, -OC(O)OR5C, -C(O)NR5AR5B, -OC(O)NR5AR5B, -OR5D, -SR5D, -NR5ASO2R5D, -NR5AC(O)R5C, -NR5AC(O)OR5C, -NR5AOR5C, -P(O)2(OR5A), -OP(O)2(OR5A), -OP(R5A)(R5B), -BR5AR5B, -SiR5AR5BR5C, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, or 2 to 3 membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted or unsubstituted aryl (e.g., C6-C10 or phenyl), or substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered).

[0174] Each R6is independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4- C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted or unsubstituted aryl (e.g., C6-C10 or phenyl), or substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered).

[0175] Each R5A, R5B, R5C, and R5Dis independently hydrogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1- C2), substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, or 2 to 3 membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4- C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted or unsubstituted aryl (e.g., C6-C10 or phenyl), or substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5to 9 membered, or 5 to 6 membered); or R5Aand R5Bsubstituents bonded to the same nitrogen atom are joined to form a substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered) or substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered).

[0176] Each X5is independently –Cl, -Br, -I, or –F.

[0177] The symbol n5 is 0, 1, 2, 3, or 4.

[0178] Each m5 and v5 is independently 1 or 2.

[0179] The symbol z5 is 0, 1, 2, or 3.

[0180] In embodiments, the homogeneous dehydrogenating catalyst has the formula:. M, L1, L2, R3, R4, and R5are as described herein, including in embodiments.

[0181] In embodiments, M is Ir, Rh, or Ru. In embodiments, M is Ir. In embodiments, M is Rh. In embodiments, M is Ru. In embodiments, M is Os.

[0182] In embodiments, a substituted L1(e.g., substituted alkylene) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted L1is substituted with a plurality of groups selected from substituent groups, size- limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when L1is substituted, it is substituted with at least one substituent group. In embodiments, when L1is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when L1is substituted, it is substituted with at least one lower substituent group.

[0183] In embodiments, L1is –O-, -S-, -NR6-, or unsubstituted C1-C10 alkylene. In embodiments, L1is –O-. In embodiments, L1is -S-. In embodiments, L1is -NR6-. In embodiments, L1is -NH-. In embodiments, L1is unsubstituted C1-C10alkylene. Inembodiments, L1is unsubstituted methylene. In embodiments, L1is unsubstituted ethylene. In embodiments, L1is unsubstituted propylene. In embodiments, L1is unsubstituted n-propylene. In embodiments, L1is unsubstituted isopropylene. In embodiments, L1is unsubstituted butylene. In embodiments, L1is unsubstituted n-butylene. In embodiments, L1is unsubstituted isobutylene. In embodiments, L1is unsubstituted tert-butylene. In embodiments, L1is substituted C1-C10alkylene. In embodiments, L1is substituted methylene. In embodiments, L1is substituted ethylene. In embodiments, L1is substituted propylene. In embodiments, L1is substituted n-propylene. In embodiments, L1is substituted isopropylene. In embodiments, L1is substituted butylene. In embodiments, L1is substituted n-butylene. In embodiments, L1is substituted isobutylene. In embodiments, L1is substituted tert-butylene. In embodiments, the substituted alkylene is substituted with a substituent group.

[0184] In embodiments, a substituted L2(e.g., substituted alkylene) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted L2is substituted with a plurality of groups selected from substituent groups, size- limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when L2is substituted, it is substituted with at least one substituent group. In embodiments, when L2is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when L2is substituted, it is substituted with at least one lower substituent group.

[0185] In embodiments, L2is –O-, -S-, -NR6-, or unsubstituted C1-C10alkylene. In embodiments, L2is –O-. In embodiments, L2is -S-. In embodiments, L2is -NR6-. In embodiments, L2is -NH-. In embodiments, L2is unsubstituted C1-C10 alkylene. In embodiments, L2is unsubstituted methylene. In embodiments, L2is unsubstituted ethylene. In embodiments, L2is unsubstituted propylene. In embodiments, L2is unsubstituted n-propylene. In embodiments, L2is unsubstituted isopropylene. In embodiments, L2is unsubstituted butylene. In embodiments, L2is unsubstituted n-butylene. In embodiments, L2is unsubstituted isobutylene. In embodiments, L2is unsubstituted tert-butylene. In embodiments, L2is substituted C1-C10 alkylene. In embodiments, L2is substituted methylene. In embodiments, L2is substituted ethylene. In embodiments, L2is substituted propylene. In embodiments, L2is substituted n-propylene. In embodiments, L2is substituted isopropylene. In embodiments, L2issubstituted butylene. In embodiments, L2is substituted n-butylene. In embodiments, L2is substituted isobutylene. In embodiments, L2is substituted tert-butylene. In embodiments, the substituted alkylene is substituted with a substituent group.

[0186] In embodiments, a substituted R3(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R3is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R3is substituted, it is substituted with at least one substituent group. In embodiments, when R3is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R3is substituted, it is substituted with at least one lower substituent group.

[0187] In embodiments, R3is unsubstituted C1-C10alkyl, unsubstituted 2 to 10 membered heteroalkyl, unsubstituted C3-C10 cycloalkyl, or unsubstituted phenyl. In embodiments, R3is unsubstituted C1-C10alkyl. In embodiments, R3is unsubstituted methyl. In embodiments, R3is unsubstituted ethyl. In embodiments, R3is unsubstituted propyl. In embodiments, R3is unsubstituted n-propyl. In embodiments, R3is unsubstituted isopropyl. In embodiments, R3is unsubstituted butyl. In embodiments, R3is unsubstituted n-butyl. In embodiments, R3is unsubstituted isobutyl. In embodiments, R3is unsubstituted tert-butyl. In embodiments, R3is unsubstituted neopentyl. In embodiments, R3is unsubstituted 2 to 10 membered heteroalkyl. In embodiments, R3is unsubstituted methoxy. In embodiments, R3is unsubstituted ethoxy. In embodiments, R3is unsubstituted propoxy. In embodiments, R3is independently n-propoxy. In embodiments, R3is unsubstituted isopropoxy. In embodiments, R3is unsubstituted butoxy. In embodiments, R3is unsubstituted n-butoxy. In embodiments, R3is unsubstituted isobutoxy. In embodiments, R3is unsubstituted tert-butoxy. In embodiments, R3is unsubstituted C3-C10cycloalkyl. In embodiments, R3is unsubstituted adamantyl. In embodiments, R3is unsubstituted 1-adamantyl. In embodiments, R3is unsubstituted 2-adamantyl. In embodiments, R3is unsubstituted phenyl.

[0188] In embodiments, a substituted R4(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R4is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R4is substituted, it is substituted with at least one substituent group. In embodiments, when R4is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R4is substituted, it is substituted with at least one lower substituent group.

[0189] In embodiments, R4is unsubstituted C1-C10 alkyl, unsubstituted 2 to 10 membered heteroalkyl, unsubstituted C3-C10 cycloalkyl, or unsubstituted phenyl. In embodiments, R4is unsubstituted C1-C10alkyl. In embodiments, R4is unsubstituted methyl. In embodiments, R4is unsubstituted ethyl. In embodiments, R4is unsubstituted propyl. In embodiments, R4is unsubstituted n-propyl. In embodiments, R4is unsubstituted isopropyl. In embodiments, R4is unsubstituted butyl. In embodiments, R4is unsubstituted n-butyl. In embodiments, R4is unsubstituted isobutyl. In embodiments, R4is unsubstituted tert-butyl. In embodiments, R4is unsubstituted neopentyl. In embodiments, R4is unsubstituted 2 to 10 membered heteroalkyl. In embodiments, R4is unsubstituted methoxy. In embodiments, R4is unsubstituted ethoxy. In embodiments, R4is unsubstituted propoxy. In embodiments, R4is independently n-propoxy. In embodiments, R4is unsubstituted isopropoxy. In embodiments, R4is unsubstituted butoxy. In embodiments, R4is unsubstituted n-butoxy. In embodiments, R4is unsubstituted isobutoxy. In embodiments, R4is unsubstituted tert-butoxy. In embodiments, R4is unsubstituted C3-C10cycloalkyl. In embodiments, R4is unsubstituted adamantyl. In embodiments, R4is unsubstituted 1-adamantyl. In embodiments, R4is unsubstituted 2-adamantyl. In embodiments, R4is unsubstituted phenyl.

[0190] In embodiments, a substituted R5(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R5is substituted with a plurality of groupsselected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R5is substituted, it is substituted with at least one substituent group. In embodiments, when R5is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R5is substituted, it is substituted with at least one lower substituent group.

[0191] In embodiments, R5is independently halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NHNH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH2F, -OCH2I, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted or unsubstituted aryl (e.g., C6-C10 or phenyl), or substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 5 membered, or 5 to 6 membered).

[0192] In embodiments, R5is independently halogen. In embodiments, R5is independently –F. In embodiments, R5is independently –Cl. In embodiments, R5is independently –Br. In embodiments, R5is independently –I. In embodiments, R5is independently -CCl3. In embodiments, R5is independently -CBr3. In embodiments, R5is independently -CF3. In embodiments, R5is independently -CI3. In embodiments, R5is independently -CH2Cl. In embodiments, R5is independently -CH2Br. In embodiments, R5is independently -CH2F. In embodiments, R5is independently -CH2I. In embodiments, R5is independently -CHCl2. In embodiments, R5is independently -CHBr2. In embodiments, R5is independently -CHF2. In embodiments, R5is independently -CHI2. In embodiments, R5is independently –CN. In embodiments, R5is independently –OR5D. In embodiments, R5is independently –OCH3. In embodiments, R5is independently –OH. In embodiments, R5is independently -NH2. In embodiments, R5is independently –COOH. In embodiments, R5is independently -CONH2. Inembodiments, R5is independently -NO2. In embodiments, R5is independently –SH. In embodiments, R5is independently -SO3H. In embodiments, R5is independently -OSO3H. In embodiments, R5is independently -SO2NH2. In embodiments, R5is independently ^NHNH2. In embodiments, R5is independently ^ONH2. In embodiments, R5is independently ^NHC(O)NHNH2. In embodiments, R5is independently ^NHC(O)NH2. In embodiments, R5is independently -NHSO2H. In embodiments, R5is independently -NHC(O)H. In embodiments, R5is independently -NHC(O)OH. In embodiments, R5is independently –NHOH. In embodiments, R5is independently -OCCl3. In embodiments, R5is independently -OCBr3. In embodiments, R5is independently -OCF3. In embodiments, R5is independently -OCI3. In embodiments, R5is independently -OCH2Cl. In embodiments, R5is independently -OCH2Br. In embodiments, R5is independently -OCH2F. In embodiments, R5is independently -OCH2I. In embodiments, R5is independently -OCHCl2. In embodiments, R5is independently -OCHBr2. In embodiments, R5is independently -OCHF2. In embodiments, R5is independently -OCHI2. In embodiments, R5is independently -OP(R5A)(R5B). In embodiments, R5is independently -OP(C(CH3)3)2. In embodiments, R5is independently unsubstituted C1-C10 alkyl. In embodiments, R5is independently unsubstituted methyl. In embodiments, R5is independently unsubstituted ethyl. In embodiments, R5is independently unsubstituted propyl. In embodiments, R5is independently unsubstituted n-propyl. In embodiments, R5is independently unsubstituted isopropyl. In embodiments, R5is independently unsubstituted butyl. In embodiments, R5is independently unsubstituted n-butyl. In embodiments, R5is independently unsubstituted isobutyl. In embodiments, R5is independently unsubstituted tert-butyl. In embodiments, R5is independently unsubstituted 2 to 4 membered heteroalkyl. In embodiments, R5is independently unsubstituted methoxy. In embodiments, R5is independently unsubstituted ethoxy. In embodiments, R5is independently unsubstituted propoxy. In embodiments, R5is independently unsubstituted n-propoxy. In embodiments, R5is independently unsubstituted isopropoxy. In embodiments, R5is independently unsubstituted butoxy. In embodiments, R5is independently unsubstituted n-butoxy. In embodiments, R5is independently unsubstituted isobutoxy. In embodiments, R5is independently unsubstituted tert-butoxy.

[0193] In embodiments, a substituted R5A(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, unsubstitut aerdyl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, orlower substituent group; wherein if the substituted R5Ais substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R5Ais substituted, it is substituted with at least one substituent group. In embodiments, when R5Ais substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R5Ais substituted, it is substituted with at least one lower substituent group.

[0194] In embodiments, a substituted R5B(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R5Bis substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R5Bis substituted, it is substituted with at least one substituent group. In embodiments, when R5Bis substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R5Bis substituted, it is substituted with at least one lower substituent group.

[0195] In embodiments, a substituted ring formed when R5Aand R5Bsubstituents bonded to the same nitrogen atom are joined (e.g., substituted heterocycloalkyl and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted ring formed when R5Aand R5Bsubstituents bonded to the same nitrogen atom are joined is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when the substituted ring formed when R5Aand R5Bsubstituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one substituent group. In embodiments, when the substituted ring formed when R5Aand R5Bsubstituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when the substituted ring formedwhen R5Aand R5Bsubstituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one lower substituent group.

[0196] In embodiments, a substituted R5C(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R5Cis substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R5Cis substituted, it is substituted with at least one substituent group. In embodiments, when R5Cis substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R5Cis substituted, it is substituted with at least one lower substituent group.

[0197] In embodiments, a substituted R5D(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R5Dis substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R5Dis substituted, it is substituted with at least one substituent group. In embodiments, when R5Dis substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R5Dis substituted, it is substituted with at least one lower substituent group.

[0198] In embodiments, R5Ais independently hydrogen or unsubstituted C1-C4alkyl. In embodiments, R5Ais independently hydrogen. In embodiments, R5Ais independently unsubstituted C1-C4 alkyl. In embodiments, R5Ais independently unsubstituted methyl. In embodiments, R5Ais independently unsubstituted ethyl. In embodiments, R5Ais independently unsubstituted propyl. In embodiments, R5Ais independently unsubstituted n-propyl. In embodiments, R5Ais independently unsubstituted isopropyl. In embodiments, R5Ais independently unsubstituted butyl. In embodiments, R5Ais independently unsubstituted n-butyl.In embodiments, R5Ais independently unsubstituted isobutyl. In embodiments, R5Ais independently unsubstituted tert-butyl.

[0199] In embodiments, R5Bis independently hydrogen or unsubstituted C1-C4alkyl. In embodiments, R5Bis independently hydrogen. In embodiments, R5Bis independently unsubstituted C1-C4 alkyl. In embodiments, R5Bis independently unsubstituted methyl. In embodiments, R5Bis independently unsubstituted ethyl. In embodiments, R5Bis independently unsubstituted propyl. In embodiments, R5Bis independently unsubstituted n-propyl. In embodiments, R5Bis independently unsubstituted isopropyl. In embodiments, R5Bis independently unsubstituted butyl. In embodiments, R5Bis independently unsubstituted n-butyl. In embodiments, R5Bis independently unsubstituted isobutyl. In embodiments, R5Bis independently unsubstituted tert-butyl.

[0200] In embodiments, R5Cis independently hydrogen or unsubstituted C1-C4 alkyl. In embodiments, R5Cis independently hydrogen. In embodiments, R5Cis independently unsubstituted C1-C4alkyl. In embodiments, R5Cis independently unsubstituted methyl. In embodiments, R5Cis independently unsubstituted ethyl. In embodiments, R5Cis independently unsubstituted propyl. In embodiments, R5Cis independently unsubstituted n-propyl. In embodiments, R5Cis independently unsubstituted isopropyl. In embodiments, R5Cis independently unsubstituted butyl. In embodiments, R5Cis independently unsubstituted n-butyl. In embodiments, R5Cis independently unsubstituted isobutyl. In embodiments, R5Cis independently unsubstituted tert-butyl.

[0201] In embodiments, R5Dis independently hydrogen or unsubstituted C1-C4 alkyl. In embodiments, R5Dis independently hydrogen. In embodiments, R5Dis independently unsubstituted C1-C4alkyl. In embodiments, R5Dis independently unsubstituted methyl. In embodiments, R5Dis independently unsubstituted ethyl. In embodiments, R5Dis independently unsubstituted propyl. In embodiments, R5Dis independently unsubstituted n-propyl. In embodiments, R5Dis independently unsubstituted isopropyl. In embodiments, R5Dis independently unsubstituted butyl. In embodiments, R5Dis independently unsubstituted n-butyl. In embodiments, R5Dis independently unsubstituted isobutyl. In embodiments, R5Dis independently unsubstituted tert-butyl.

[0202] In embodiments, z5 is 0. In embodiments, z5 is 1. In embodiments, z5 is 2. In embodiments, z5 is 3.

[0203] In embodiments, a substituted R6(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R6is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R6is substituted, it is substituted with at least one substituent group. In embodiments, when R6is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R6is substituted, it is substituted with at least one lower substituent group.

[0204] In embodiments, R6is independently hydrogen or unsubstituted C1-C4alkyl. In embodiments, R6is independently hydrogen. In embodiments, R6is independently unsubstituted C1-C4 alkyl. In embodiments, R6is independently unsubstituted methyl. In embodiments, R6is independently unsubstituted ethyl. In embodiments, R6is independently unsubstituted propyl. In embodiments, R6is independently unsubstituted n-propyl. In embodiments, R6is independently unsubstituted isopropyl. In embodiments, R6is independently unsubstituted butyl. In embodiments, R6is independently unsubstituted n-butyl. In embodiments, R6is independently unsubstituted isobutyl. In embodiments, R6is independently unsubstituted tert- butyl.

[0205] In embodiments, the homogeneous dehydrogenating catalyst is.

[0206] In embodiments, the dehydrogenated polymer includes at least one –C(R1)=C(R2)- monomer unit.

[0207] R1is independently hydrogen, halogen, -CX13, -CHX12, -CH2X1, -OCX13, -OCH2X1, -OCHX12, -CN, -SOn1R1D, -SOv1NR1AR1B, ^NR1CNR1AR1B, ^ONR1AR1B, -NR1CC(O)NR1AR1B, -N(O)m1, -NR1AR1B, -C(O)R1C, -C(O)OR1C, -OC(O)R1C, -OC(O)OR1C, -C(O)NR1AR1B, -OC(O)NR1AR1B, -OR1D, -SR1D, -NR1ASO2R1D, -NR1AC(O)R1C, -NR1AC(O)OR1C, -NR1AOR1C, -P(O)2(OR1A), -OP(O)2(OR1A), -BR1AR1B, -SiR1AR1BR1C, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, or 2 to 3 membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted or unsubstituted aryl (e.g., C6-C10 or phenyl), or substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered).

[0208] R2is independently hydrogen, halogen, -CX23, -CHX22, -CH2X2, -OCX23, -OCH2X2, -OCHX22, -CN, -SOn2R2D, -SOv2NR2AR2B, ^NR2CNR2AR2B, ^ONR2AR2B, -NR2CC(O)NR2AR2B, -N(O)m2, -NR2AR2B, -C(O)R2C, -C(O)OR2C, -OC(O)R2C, -OC(O)OR2C, -C(O)NR2AR2B, -OC(O)NR2AR2B, -OR2D, -SR2D, -NR2ASO2R2D, -NR2AC(O)R2C, -NR2AC(O)OR2C, -NR2AOR2C, -P(O)2(OR2A), -OP(O)2(OR2A), -BR2AR2B, -SiR2AR2BR2C, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, or 2 to 3 membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted or unsubstituted aryl (e.g., C6-C10or phenyl), or substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered).

[0209] Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, and R2Dis independently hydrogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, or 2 to 3 membered), substituted or unsubstituted cycloalkyl (e.g.,C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted or unsubstituted aryl (e.g., C6-C10or phenyl), or substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered); or R1Aand R1Bsubstituents bonded to the same nitrogen atom are joined to form a substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered) or substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered); or R2Aand R2Bsubstituents bonded to the same nitrogen atom are joined to form a substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered) or substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered).

[0210] Each X1and X2is independently –Cl, -Br, -I, or –F.

[0211] Each n1 and n2 is independently 0, 1, 2, 3, or 4.

[0212] Each m1, m2, v1, and v2 is independently 1 or 2.

[0213] In embodiments, a substituted R1(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R1is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R1is substituted, it is substituted with at least one substituent group. In embodiments, when R1is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R1is substituted, it is substituted with at least one lower substituent group.

[0214] In embodiments, R1is independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH2F, -OCH2I, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, substituted or unsubstituted alkyl (e.g.,C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, or 2 to 3 membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted or unsubstituted aryl (e.g., C6-C10 or phenyl), or substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered).

[0215] In embodiments, R1is independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH2F, -OCH2I, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, or substituted or unsubstituted C1-C20alkyl.

[0216] In embodiments, R1is independently hydrogen. In embodiments, R1is independently substituted or unsubstituted C1-C1000alkyl. In embodiments, R1is independently substituted or unsubstituted C1-C500 alkyl. In embodiments, R1is independently substituted or unsubstituted C1-C100 alkyl. In embodiments, R1is independently substituted or unsubstituted C1-C50 alkyl. In embodiments, R1is independently substituted or unsubstituted C1-C20alkyl. In embodiments, R1is independently substituted or unsubstituted C1-C10alkyl. In embodiments, R1is independently substituted or unsubstituted C1-C5 alkyl. In embodiments, R1is independently unsubstituted methyl. In embodiments, R1is independently unsubstituted ethyl. In embodiments, R1is independently unsubstituted propyl. In embodiments, R1is independently unsubstituted n- propyl. In embodiments, R1is independently unsubstituted isopropyl. In embodiments, R1is independently unsubstituted butyl. In embodiments, R1is independently unsubstituted n-butyl. In embodiments, R1is independently unsubstituted tert-butyl.

[0217] In embodiments, a substituted R1A(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R1Ais substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group mayoptionally be different. In embodiments, when R1Ais substituted, it is substituted with at least one substituent group. In embodiments, when R1Ais substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R1Ais substituted, it is substituted with at least one lower substituent group.

[0218] In embodiments, a substituted R1B(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R1Bis substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R1Bis substituted, it is substituted with at least one substituent group. In embodiments, when R1Bis substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R1Bis substituted, it is substituted with at least one lower substituent group.

[0219] In embodiments, a substituted ring formed when R1Aand R1Bsubstituents bonded to the same nitrogen atom are joined (e.g., substituted heterocycloalkyl and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted ring formed when R1Aand R1Bsubstituents bonded to the same nitrogen atom are joined is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when the substituted ring formed when R1Aand R1Bsubstituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one substituent group. In embodiments, when the substituted ring formed when R1Aand R1Bsubstituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when the substituted ring formed when R1Aand R1Bsubstituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one lower substituent group.

[0220] In embodiments, a substituted R1C(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substitutedheteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R1Cis substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R1Cis substituted, it is substituted with at least one substituent group. In embodiments, when R1Cis substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R1Cis substituted, it is substituted with at least one lower substituent group.

[0221] In embodiments, a substituted R1D(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R1Dis substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R1Dis substituted, it is substituted with at least one substituent group. In embodiments, when R1Dis substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R1Dis substituted, it is substituted with at least one lower substituent group.

[0222] In embodiments, R1Ais independently hydrogen. In embodiments, R1Ais independently substituted or unsubstituted C1-C5alkyl. In embodiments, R1Ais independently unsubstituted methyl. In embodiments, R1Ais independently unsubstituted ethyl. In embodiments, R1Ais independently unsubstituted propyl. In embodiments, R1Ais independently unsubstituted n-propyl. In embodiments, R1Ais independently unsubstituted isopropyl. In embodiments, R1Ais independently unsubstituted butyl. In embodiments, R1Ais independently unsubstituted n-butyl. In embodiments, R1Ais independently unsubstituted tert-butyl.

[0223] In embodiments, R1Bis independently hydrogen. In embodiments, R1Bis independently substituted or unsubstituted C1-C5alkyl. In embodiments, R1Bis independently unsubstituted methyl. In embodiments, R1Bis independently unsubstituted ethyl. In embodiments, R1Bis independently unsubstituted propyl. In embodiments, R1Bis independently unsubstituted n-propyl. In embodiments, R1Bis independently unsubstituted isopropyl. Inembodiments, R1Bis independently unsubstituted butyl. In embodiments, R1Bis independently unsubstituted n-butyl. In embodiments, R1Bis independently unsubstituted tert-butyl.

[0224] In embodiments, R1Cis independently hydrogen. In embodiments, R1Cis independently substituted or unsubstituted C1-C5 alkyl. In embodiments, R1Cis independently unsubstituted methyl. In embodiments, R1Cis independently unsubstituted ethyl. In embodiments, R1Cis independently unsubstituted propyl. In embodiments, R1Cis independently unsubstituted n-propyl. In embodiments, R1Cis independently unsubstituted isopropyl. In embodiments, R1Cis independently unsubstituted butyl. In embodiments, R1Cis independently unsubstituted n-butyl. In embodiments, R1Cis independently unsubstituted tert-butyl.

[0225] In embodiments, R1Dis independently hydrogen. In embodiments, R1Dis independently substituted or unsubstituted C1-C5 alkyl. In embodiments, R1Dis independently unsubstituted methyl. In embodiments, R1Dis independently unsubstituted ethyl. In embodiments, R1Dis independently unsubstituted propyl. In embodiments, R1Dis independently unsubstituted n-propyl. In embodiments, R1Dis independently unsubstituted isopropyl. In embodiments, R1Dis independently unsubstituted butyl. In embodiments, R1Dis independently unsubstituted n-butyl. In embodiments, R1Dis independently unsubstituted tert-butyl.

[0226] In embodiments, a substituted R2(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R2is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R2is substituted, it is substituted with at least one substituent group. In embodiments, when R2is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R2is substituted, it is substituted with at least one lower substituent group.

[0227] In embodiments, R2is independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br,-OCH2F, -OCH2I, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, or 2 to 3 membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted or unsubstituted aryl (e.g., C6-C10or phenyl), or substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered).

[0228] In embodiments, R2is independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH2F, -OCH2I, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, or substituted or unsubstituted C1-C20 alkyl.

[0229] In embodiments, R2is independently hydrogen. In embodiments, R2is independently substituted or unsubstituted C1-C1000 alkyl. In embodiments, R2is independently substituted or unsubstituted C1-C500 alkyl. In embodiments, R2is independently substituted or unsubstituted C1-C100alkyl. In embodiments, R2is independently substituted or unsubstituted C1-C50alkyl. In embodiments, R2is independently substituted or unsubstituted C1-C20alkyl. In embodiments, R2is independently substituted or unsubstituted C1-C10 alkyl. In embodiments, R2is independently substituted or unsubstituted C1-C5 alkyl. In embodiments, R2is independently unsubstituted methyl. In embodiments, R2is independently unsubstituted ethyl. In embodiments, R2is independently unsubstituted propyl. In embodiments, R2is independently unsubstituted n- propyl. In embodiments, R2is independently unsubstituted isopropyl. In embodiments, R2is independently unsubstituted butyl. In embodiments, R2is independently unsubstituted n-butyl. In embodiments, R2is independently unsubstituted tert-butyl.

[0230] In embodiments, a substituted R2A(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R2Ais substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups;each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R2Ais substituted, it is substituted with at least one substituent group. In embodiments, when R2Ais substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R2Ais substituted, it is substituted with at least one lower substituent group.

[0231] In embodiments, a substituted R2B(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R2Bis substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R2Bis substituted, it is substituted with at least one substituent group. In embodiments, when R2Bis substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R2Bis substituted, it is substituted with at least one lower substituent group.

[0232] In embodiments, a substituted ring formed when R2Aand R2Bsubstituents bonded to the same nitrogen atom are joined (e.g., substituted heterocycloalkyl and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted ring formed when R2Aand R2Bsubstituents bonded to the same nitrogen atom are joined is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when the substituted ring formed when R2Aand R2Bsubstituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one substituent group. In embodiments, when the substituted ring formed when R2Aand R2Bsubstituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when the substituted ring formed when R2Aand R2Bsubstituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one lower substituent group.

[0233] In embodiments, a substituted R2C(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R2Cis substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R2Cis substituted, it is substituted with at least one substituent group. In embodiments, when R2Cis substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R2Cis substituted, it is substituted with at least one lower substituent group.

[0234] In embodiments, a substituted R2D(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and / or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R2Dis substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and / or lower substituent group may optionally be different. In embodiments, when R2Dis substituted, it is substituted with at least one substituent group. In embodiments, when R2Dis substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R2Dis substituted, it is substituted with at least one lower substituent group.

[0235] In embodiments, R2Ais independently hydrogen. In embodiments, R2Ais independently substituted or unsubstituted C1-C5 alkyl. In embodiments, R2Ais independently unsubstituted methyl. In embodiments, R2Ais independently unsubstituted ethyl. In embodiments, R2Ais independently unsubstituted propyl. In embodiments, R2Ais independently unsubstituted n-propyl. In embodiments, R2Ais independently unsubstituted isopropyl. In embodiments, R2Ais independently unsubstituted butyl. In embodiments, R2Ais independently unsubstituted n-butyl. In embodiments, R2Ais independently unsubstituted tert-butyl.

[0236] In embodiments, R2Bis independently hydrogen. In embodiments, R2Bis independently substituted or unsubstituted C1-C5 alkyl. In embodiments, R2Bis independently unsubstituted methyl. In embodiments, R2Bis independently unsubstituted ethyl. Inembodiments, R2Bis independently unsubstituted propyl. In embodiments, R2Bis independently unsubstituted n-propyl. In embodiments, R2Bis independently unsubstituted isopropyl. In embodiments, R2Bis independently unsubstituted butyl. In embodiments, R2Bis independently unsubstituted n-butyl. In embodiments, R2Bis independently unsubstituted tert-butyl.

[0237] In embodiments, R2Cis independently hydrogen. In embodiments, R2Cis independently substituted or unsubstituted C1-C5alkyl. In embodiments, R2Cis independently unsubstituted methyl. In embodiments, R2Cis independently unsubstituted ethyl. In embodiments, R2Cis independently unsubstituted propyl. In embodiments, R2Cis independently unsubstituted n-propyl. In embodiments, R2Cis independently unsubstituted isopropyl. In embodiments, R2Cis independently unsubstituted butyl. In embodiments, R2Cis independently unsubstituted n-butyl. In embodiments, R2Cis independently unsubstituted tert-butyl.

[0238] In embodiments, R2Dis independently hydrogen. In embodiments, R2Dis independently substituted or unsubstituted C1-C5alkyl. In embodiments, R2Dis independently unsubstituted methyl. In embodiments, R2Dis independently unsubstituted ethyl. In embodiments, R2Dis independently unsubstituted propyl. In embodiments, R2Dis independently unsubstituted n-propyl. In embodiments, R2Dis independently unsubstituted isopropyl. In embodiments, R2Dis independently unsubstituted butyl. In embodiments, R2Dis independently unsubstituted n-butyl. In embodiments, R2Dis independently unsubstituted tert-butyl.

[0239] In embodiments, the method is conducted under continuous flow conditions.

[0240] In embodiments, when R1is substituted, R1is substituted with one or more first substituent groups denoted by R1.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R1.1substituent group is substituted, the R1.1substituent group is substituted with one or more second substituent groups denoted by R1.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R1.2substituent group is substituted, the R1.2substituent group is substituted with one or more third substituent groups denoted by R1.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R1, R1.1, R1.2, and R1.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of“first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R1, R1.1, R1.2, and R1.3, respectively.

[0241] In embodiments, when R1Ais substituted, R1Ais substituted with one or more first substituent groups denoted by R1A.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R1A.1substituent group is substituted, the R1A.1substituent group is substituted with one or more second substituent groups denoted by R1A.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R1A.2substituent group is substituted, the R1A.2substituent group is substituted with one or more third substituent groups denoted by R1A.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R1A, R1A.1, R1A.2, and R1A.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R1A, R1A.1, R1A.2, and R1A.3, respectively.

[0242] In embodiments, when R1Bis substituted, R1Bis substituted with one or more first substituent groups denoted by R1B.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R1B.1substituent group is substituted, the R1B.1substituent group is substituted with one or more second substituent groups denoted by R1B.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R1B.2substituent group is substituted, the R1B.2substituent group is substituted with one or more third substituent groups denoted by R1B.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R1B, R1B.1, R1B.2, and R1B.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R1B, R1B.1, R1B.2, and R1B.3, respectively.

[0243] In embodiments, when R1Aand R1Bsubstituents bonded to the same nitrogen atom are optionally joined to form a moiety that is substituted (e.g., a substituted heterocycloalkyl or substituted heteroaryl), the moiety is substituted with one or more first substituent groups denoted by R1A.1as explained in the definitions section above in the description of “firstsubstituent group(s)”. In embodiments, when an R1A.1substituent group is substituted, the R1A.1substituent group is substituted with one or more second substituent groups denoted by R1A.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R1A.2substituent group is substituted, the R1A.2substituent group is substituted with one or more third substituent groups denoted by R1A.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R1A.1, R1A.2, and R1A.3have values corresponding to the values of RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW.1, RWW.2, and RWW.3correspond to R1A.1, R1A.2, and R1A.3, respectively.

[0244] In embodiments, when R1Aand R1Bsubstituents bonded to the same nitrogen atom are optionally joined to form a moiety that is substituted (e.g., a substituted heterocycloalkyl or substituted heteroaryl), the moiety is substituted with one or more first substituent groups denoted by R1B.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R1B.1substituent group is substituted, the R1B.1substituent group is substituted with one or more second substituent groups denoted by R1B.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R1B.2substituent group is substituted, the R1B.2substituent group is substituted with one or more third substituent groups denoted by R1B.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R1B.1, R1B.2, and R1B.3have values corresponding to the values of RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW.1, RWW.2, and RWW.3correspond to R1B.1, R1B.2, and R1B.3, respectively.

[0245] In embodiments, when R1Cis substituted, R1Cis substituted with one or more first substituent groups denoted by R1C.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R1C.1substituent group is substituted, the R1C.1substituent group is substituted with one or more second substituent groups denoted by R1C.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R1C.2substituent group is substituted, the R1C.2substituent group is substituted with one or more third substituent groups denoted by R1C.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R1C, R1C.1, R1C.2, and R1C.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R1C, R1C.1, R1C.2, and R1C.3, respectively.

[0246] In embodiments, when R1Dis substituted, R1Dis substituted with one or more first substituent groups denoted by R1D.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R1D.1substituent group is substituted, the R1D.1substituent group is substituted with one or more second substituent groups denoted by R1D.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R1D.2substituent group is substituted, the R1D.2substituent group is substituted with one or more third substituent groups denoted by R1D.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R1D, R1D.1, R1D.2, and R1D.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R1D, R1D.1, R1D.2, and R1D.3, respectively.

[0247] In embodiments, when R2is substituted, R2is substituted with one or more first substituent groups denoted by R2.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2.1substituent group is substituted, the R2.1substituent group is substituted with one or more second substituent groups denoted by R2.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2.2substituent group is substituted, the R2.2substituent group is substituted with one or more third substituent groups denoted by R2.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R2, R2.1, R2.2, and R2.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R2, R2.1, R2.2, and R2.3, respectively.

[0248] In embodiments, when R2Ais substituted, R2Ais substituted with one or more first substituent groups denoted by R2A.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2A.1substituent group is substituted, the R2A.1substituent group is substituted with one or more second substituent groups denoted by R2A.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2A.2substituent group is substituted, the R2A.2substituent group is substituted with one or more third substituent groups denoted by R2A.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R2A, R2A.1, R2A.2, and R2A.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R2A, R2A.1, R2A.2, and R2A.3, respectively.

[0249] In embodiments, when R2Bis substituted, R2Bis substituted with one or more first substituent groups denoted by R2B.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2B.1substituent group is substituted, the R2B.1substituent group is substituted with one or more second substituent groups denoted by R2B.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2B.2substituent group is substituted, the R2B.2substituent group is substituted with one or more third substituent groups denoted by R2B.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R2B, R2B.1, R2B.2, and R2B.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R2B, R2B.1, R2B.2, and R2B.3, respectively.

[0250] In embodiments, when R2Aand R2Bsubstituents bonded to the same nitrogen atom are optionally joined to form a moiety that is substituted (e.g., a substituted heterocycloalkyl or substituted heteroaryl), the moiety is substituted with one or more first substituent groups denoted by R2A.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2A.1substituent group is substituted, the R2A.1substituent group is substituted with one or more second substituent groups denoted by R2A.2asexplained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2A.2substituent group is substituted, the R2A.2substituent group is substituted with one or more third substituent groups denoted by R2A.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R2A.1, R2A.2, and R2A.3have values corresponding to the values of RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW.1, RWW.2, and RWW.3correspond to R2A.1, R2A.2, and R2A.3, respectively.

[0251] In embodiments, when R2Aand R2Bsubstituents bonded to the same nitrogen atom are optionally joined to form a moiety that is substituted (e.g., a substituted heterocycloalkyl or substituted heteroaryl), the moiety is substituted with one or more first substituent groups denoted by R2B.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2B.1substituent group is substituted, the R2B.1substituent group is substituted with one or more second substituent groups denoted by R2B.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2B.2substituent group is substituted, the R2B.2substituent group is substituted with one or more third substituent groups denoted by R2B.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R2B.1, R2B.2, and R2B.3have values corresponding to the values of RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW.1, RWW.2, and RWW.3correspond to R2B.1, R2B.2, and R2B.3, respectively.

[0252] In embodiments, when R2Cis substituted, R2Cis substituted with one or more first substituent groups denoted by R2C.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2C.1substituent group is substituted, the R2C.1substituent group is substituted with one or more second substituent groups denoted by R2C.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2C.2substituent group is substituted, the R2C.2substituent group is substituted with one or more third substituent groups denoted by R2C.3as explained in the definitions section above in the description of “first substituent group(s)”. In theabove embodiments, R2C, R2C.1, R2C.2, and R2C.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R2C, R2C.1, R2C.2, and R2C.3, respectively.

[0253] In embodiments, when R2Dis substituted, R2Dis substituted with one or more first substituent groups denoted by R2D.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2D.1substituent group is substituted, the R2D.1substituent group is substituted with one or more second substituent groups denoted by R2D.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R2D.2substituent group is substituted, the R2D.2substituent group is substituted with one or more third substituent groups denoted by R2D.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R2D, R2D.1, R2D.2, and R2D.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R2D, R2D.1, R2D.2, and R2D.3, respectively.

[0254] In embodiments, when R3is substituted, R3is substituted with one or more first substituent groups denoted by R3.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R3.1substituent group is substituted, the R3.1substituent group is substituted with one or more second substituent groups denoted by R3.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R3.2substituent group is substituted, the R3.2substituent group is substituted with one or more third substituent groups denoted by R3.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R3, R3.1, R3.2, and R3.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R3, R3.1, R3.2, and R3.3, respectively.

[0255] In embodiments, when R4is substituted, R4is substituted with one or more first substituent groups denoted by R4.1as explained in the definitions section above in the descriptionof “first substituent group(s)”. In embodiments, when an R4.1substituent group is substituted, the R4.1substituent group is substituted with one or more second substituent groups denoted by R4.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R4.2substituent group is substituted, the R4.2substituent group is substituted with one or more third substituent groups denoted by R4.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R4, R4.1, R4.2, and R4.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R4, R4.1, R4.2, and R4.3, respectively.

[0256] In embodiments, when R5is substituted, R5is substituted with one or more first substituent groups denoted by R5.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5.1substituent group is substituted, the R5.1substituent group is substituted with one or more second substituent groups denoted by R5.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5.2substituent group is substituted, the R5.2substituent group is substituted with one or more third substituent groups denoted by R5.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R5, R5.1, R5.2, and R5.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R5, R5.1, R5.2, and R5.3, respectively.

[0257] In embodiments, when R5Ais substituted, R5Ais substituted with one or more first substituent groups denoted by R5A.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5A.1substituent group is substituted, the R5A.1substituent group is substituted with one or more second substituent groups denoted by R5A.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5A.2substituent group is substituted, the R5A.2substituent group is substituted with one or more third substituent groups denoted by R5A.3as explained in the definitions section above in the description of “first substituent group(s)”. In theabove embodiments, R5A, R5A.1, R5A.2, and R5A.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R5A, R5A.1, R5A.2, and R5A.3, respectively.

[0258] In embodiments, when R5Bis substituted, R5Bis substituted with one or more first substituent groups denoted by R5B.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5B.1substituent group is substituted, the R5B.1substituent group is substituted with one or more second substituent groups denoted by R5B.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5B.2substituent group is substituted, the R5B.2substituent group is substituted with one or more third substituent groups denoted by R5B.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R5B, R5B.1, R5B.2, and R5B.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R5B, R5B.1, R5B.2, and R5B.3, respectively.

[0259] In embodiments, when R5Aand R5Bsubstituents bonded to the same nitrogen atom are optionally joined to form a moiety that is substituted (e.g., a substituted heterocycloalkyl or substituted heteroaryl), the moiety is substituted with one or more first substituent groups denoted by R5A.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5A.1substituent group is substituted, the R5A.1substituent group is substituted with one or more second substituent groups denoted by R5A.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5A.2substituent group is substituted, the R5A.2substituent group is substituted with one or more third substituent groups denoted by R5A.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R5A.1, R5A.2, and R5A.3have values corresponding to the values of RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW.1, RWW.2, and RWW.3correspond to R5A.1, R5A.2, and R5A.3, respectively.

[0260] In embodiments, when R5Aand R5Bsubstituents bonded to the same nitrogen atom are optionally joined to form a moiety that is substituted (e.g., a substituted heterocycloalkyl or substituted heteroaryl), the moiety is substituted with one or more first substituent groups denoted by R5B.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5B.1substituent group is substituted, the R5B.1substituent group is substituted with one or more second substituent groups denoted by R5B.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5B.2substituent group is substituted, the R5B.2substituent group is substituted with one or more third substituent groups denoted by R5B.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R5B.1, R5B.2, and R5B.3have values corresponding to the values of RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW.1, RWW.2, and RWW.3correspond to R5B.1, R5B.2, and R5B.3, respectively.

[0261] In embodiments, when R5Cis substituted, R5Cis substituted with one or more first substituent groups denoted by R5C.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5C.1substituent group is substituted, the R5C.1substituent group is substituted with one or more second substituent groups denoted by R5C.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5C.2substituent group is substituted, the R5C.2substituent group is substituted with one or more third substituent groups denoted by R5C.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R5C, R5C.1, R5C.2, and R5C.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R5C, R5C.1, R5C.2, and R5C.3, respectively.

[0262] In embodiments, when R5Dis substituted, R5Dis substituted with one or more first substituent groups denoted by R5D.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5D.1substituent group is substituted, the R5D.1substituent group is substituted with one or more second substituent groupsdenoted by R5D.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R5D.2substituent group is substituted, the R5D.2substituent group is substituted with one or more third substituent groups denoted by R5D.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R5D, R5D.1, R5D.2, and R5D.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R5D, R5D.1, R5D.2, and R5D.3, respectively.

[0263] In embodiments, when R6is substituted, R6is substituted with one or more first substituent groups denoted by R6.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R6.1substituent group is substituted, the R6.1substituent group is substituted with one or more second substituent groups denoted by R6.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R6.2substituent group is substituted, the R6.2substituent group is substituted with one or more third substituent groups denoted by R6.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, R6, R6.1, R6.2, and R6.3have values corresponding to the values of RWW, RWW.1, RWW.2, and RWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein RWW, RWW.1, RWW.2, and RWW.3correspond to R6, R6.1, R6.2, and R6.3, respectively.

[0264] In embodiments, when L1is substituted, L1is substituted with one or more first substituent groups denoted by RL1.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an RL1.1substituent group is substituted, the RL1.1substituent group is substituted with one or more second substituent groups denoted by RL1.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an RL1.2substituent group is substituted, the RL1.2substituent group is substituted with one or more third substituent groups denoted by RL1.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, L1, RL1.1, RL1.2, and RL1.3have values corresponding to the values of LWW, RLWW.1, RLWW.2, and RLWW.3, respectively, as explained in the definitions section above in thedescription of “first substituent group(s)”, wherein LWW, RLWW.1, RLWW.2, and RLWW.3, RL1.1, RL1.2, and RL1.3, respectively.

[0265] In embodiments, when L2is substituted, L2is substituted with one or more first substituent groups denoted by RL2.1as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an RL2.1substituent group is substituted, the RL2.1substituent group is substituted with one or more second substituent groups denoted by RL2.2as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an RL2.2substituent group is substituted, the RL2.2substituent group is substituted with one or more third substituent groups denoted by RL2.3as explained in the definitions section above in the description of “first substituent group(s)”. In the above embodiments, L2, RL2.1, RL2.2, and RL2.3have values corresponding to the values of LWW, RLWW.1, RLWW.2, and RLWW.3, respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein LWW, RLWW.1, RLWW.2, and RLWW.3are L2, RL2.1, RL2.2, and RL2.3, respectively.

[0266] In an aspect is provided a method of quantifying propene, the method including (a) conducting a chemical reaction that produces propene in the presence of a gaseous internal standard at a known pressure; (b) analyzing a crude reaction mixture produced by the chemical reaction by gas chromatography; (c) measuring the signal intensities. III. Compositions

[0267] In an aspect is provided a substituted or unsubstituted dehydrogenated polyolefin. In an aspect is provided a substituted or substituted dehydrogenated polyethylene or polypropylene. In an aspect the dehydrogenated polyethylene is produced by dehydrogenation of polyethylene. Alternatively, in some embodiments, the dehydrogenated polyethylene is not produced by dehydrogenation of polyethylene. In some embodiments, the dehydrogenated polyethylene is produced by installation of a leaving group followed by elimination. In some embodiiments, the dehydrogenated polyethylene is produced by fragmentation of a precursor into fragments (e.g., cracking, pyrolysis, fluid catalytic cracking, catalytic cracking). In some emboidments, the dehydrogenation polyethylene comprises an olefin moiety. In an aspect is provided a substituted or unsubstituted dehydrogenated polyethylene, wherein a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units areunsaturated (e.g., olefinic, e.g., monoenes). In embodiments, a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units are olefinic. In embodiments, a percentage of from 0.01% to 1.5% of monomer units are olefinic. In embodiments, a percentage of from 1.7% to 2.3% of monomer units are olefinic. In embodiments, a percentage of from 1.7% to 2.3% of monomer units are olefinic. In embodiments, a percentage of from 2.4% to 4.3% of monomer units are olefinic. In embodiments, a percentage of from 4.5% to 13.2% of monomer units are olefinic.

[0268] In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least 0.001%, at least 0.01%, at least 0.1%, at least 0.2%, at least 0.5%, at least 0.75%, at least 0.9%, at least 1%, at least 1.1%, at least 1.3%, at least 1.5%, or more. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most 0.001%, at most 0.01%, at most 0.1%, at most 0.2%, at most 0.5%, at most 0.75%, at most 0.9%, at most 1%, at most 1.1%, at most 1.3%, at most 1.5%, or less.

[0269] In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 0.001% to about 1.5%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least about 0.001%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most about 1.5%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 0.001% to about 0.01%, about 0.001% to about 0.1%, about 0.001% to about 0.2%, about 0.001% to about 0.5%, about 0.001% to about 0.75%, about 0.001% to about 0.9%, about 0.001% to about 1%, about 0.001% to about 1.1%, about 0.001% to about 1.3%, about 0.001% to about 1.4%, about 0.001% to about 1.5%, about 0.01% to about 0.1%, about 0.01% to about 0.2%, about 0.01% to about 0.5%, about 0.01% to about 0.75%, about 0.01% to about 0.9%, about 0.01% to about 1%, about 0.01% to about 1.1%, about 0.01% to about 1.3%, about 0.01% to about 1.4%, about 0.01% to about 1.5%, about 0.1% to about 0.2%, about 0.1% to about 0.5%, about 0.1% to about 0.75%, about 0.1% to about 0.9%, about 0.1% to about 1%, about 0.1% to about 1.1%, about 0.1% to about 1.3%, about 0.1% to about 1.4%, about 0.1% to about 1.5%, about 0.2% to about 0.5%, about 0.2% to about 0.75%, about 0.2% to about 0.9%, about 0.2% to about 1%, about 0.2% to about 1.1%, about 0.2% to about 1.3%, about 0.2% to about 1.4%, about 0.2% to about 1.5%, about 0.5% to about 0.75%, about 0.5% to about 0.9%, about 0.5% toabout 1%, about 0.5% to about 1.1%, about 0.5% to about 1.3%, about 0.5% to about 1.4%, about 0.5% to about 1.5%, about 0.75% to about 0.9%, about 0.75% to about 1%, about 0.75% to about 1.1%, about 0.75% to about 1.3%, about 0.75% to about 1.4%, about 0.75% to about 1.5%, about 0.9% to about 1%, about 0.9% to about 1.1%, about 0.9% to about 1.3%, about 0.9% to about 1.4%, about 0.9% to about 1.5%, about 1% to about 1.1%, about 1% to about 1.3%, about 1% to about 1.4%, about 1% to about 1.5%, about 1.1% to about 1.3%, about 1.1% to about 1.4%, about 1.1% to about 1.5%, about 1.3% to about 1.4%, about 1.3% to about 1.5%, or about 1.4% to about 1.5%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 0.001%, about 0.01%, about 0.1%, about 0.2%, about 0.5%, about 0.75%, about 0.9%, about 1%, about 1.1%, about 1.3%, about 1.4%, or about 1.5%.

[0270] In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least 1.7%, at least 1.8%, at least 1.9%, at least 2.0%, at least 2.1%, at least 2.2%, at least 2.3%, or more. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most 1.7%, at most 1.8%, at most 1.9%, at most 2.0%, at most 2.1%, at most 2.2%, at most 2.3%, or less.

[0271] In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 1.7% to about 2.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least about 1.7%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most about 2.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 1.7% to about 1.8%, about 1.7% to about 1.9%, about 1.7% to about 2%, about 1.7% to about 2.1%, about 1.7% to about 2.2%, about 1.7% to about 2.3%, about 1.8% to about 1.9%, about 1.8% to about 2%, about 1.8% to about 2.1%, about 1.8% to about 2.2%, about 1.8% to about 2.3%, about 1.9% to about 2%, about 1.9% to about 2.1%, about 1.9% to about 2.2%, about 1.9% to about 2.3%, about 2% to about 2.1%, about 2% to about 2.2%, about 2% to about 2.3%, about 2.1% to about 2.2%, about 2.1% to about 2.3%, or about 2.2% to about 2.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 1.7%, about 1.8%, about 1.9%, about 2%, about 2.1%, about 2.2%, or about 2.3%.

[0272] In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least 2.4%, at least 2.5%, at least 2.6%, at least 2.7%, at least 2.8%, at least2.9%, at least 3%, at least 3.3%, at least 3.5%, at least 3.7%, at least 4%, at least 4.3%, or more. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most 2.4%, at most 2.5%, at most 2.6%, at most 2.7%, at most 2.8%, at most 2.9%, at most 3%, at most 3.3%, at most 3.5%, at most 3.7%, at most 4%, at most 4.3%, or less.In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 2.4% to about 4.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least about 2.4%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most about 4.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 2.4% to about 2.5%, about 2.4% to about 2.6%, about 2.4% to about 2.7%, about 2.4% to about 2.8%, about 2.4% to about 2.9%, about 2.4% to about 3%, about 2.4% to about 3.3%, about 2.4% to about 3.5%, about 2.4% to about 3.7%, about 2.4% to about 4%, about 2.4% to about 4.3%, about 2.5% to about 2.6%, about 2.5% to about 2.7%, about 2.5% to about 2.8%, about 2.5% to about 2.9%, about 2.5% to about 3%, about 2.5% to about 3.3%, about 2.5% to about 3.5%, about 2.5% to about 3.7%, about 2.5% to about 4%, about 2.5% to about 4.3%, about 2.6% to about 2.7%, about 2.6% to about 2.8%, about 2.6% to about 2.9%, about 2.6% to about 3%, about 2.6% to about 3.3%, about 2.6% to about 3.5%, about 2.6% to about 3.7%, about 2.6% to about 4%, about 2.6% to about 4.3%, about 2.7% to about 2.8%, about 2.7% to about 2.9%, about 2.7% to about 3%, about 2.7% to about 3.3%, about 2.7% to about 3.5%, about 2.7% to about 3.7%, about 2.7% to about 4%, about 2.7% to about 4.3%, about 2.8% to about 2.9%, about 2.8% to about 3%, about 2.8% to about 3.3%, about 2.8% to about 3.5%, about 2.8% to about 3.7%, about 2.8% to about 4%, about 2.8% to about 4.3%, about 2.9% to about 3%, about 2.9% to about 3.3%, about 2.9% to about 3.5%, about 2.9% to about 3.7%, about 2.9% to about 4%, about 2.9% to about 4.3%, about 3% to about 3.3%, about 3% to about 3.5%, about 3% to about 3.7%, about 3% to about 4%, about 3% to about 4.3%, about 3.3% to about 3.5%, about 3.3% to about 3.7%, about 3.3% to about 4%, about 3.3% to about 4.3%, about 3.5% to about 3.7%, about 3.5% to about 4%, about 3.5% to about 4.3%, about 3.7% to about 4%, about 3.7% to about 4.3%, or about 4% to about 4.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 2.4%, about 2.5%, about 2.6%, about 2.7%, about 2.8%, about 2.9%, about 3%, about 3.3%, about 3.5%, about 3.7%, about 4%, or about 4.3%.

[0273] In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least 4.5%, at least 4.7%, at least 5%, at least 5.2%, at least 5.5%, at least 6%, at least 7%, at least 8%, at least 9%, at least 10%, at least 11%, at least 12%, at least 13%, at least 13.3%, or more. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most 4.5%, at most 4.7%, at most 5%, at most 5.2%, at most 5.5%, at most 6%, at most 7%, at most 8%, at most 9%, at most 10%, at most 11%, at most 12%, at most 13%, at most 13.3%, or more.

[0274] In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 4.5% to about 13.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least about 4.5%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most about 13.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 4.5% to about 4.7%, about 4.5% to about 5%, about 4.5% to about 5.2%, about 4.5% to about 5.5%, about 4.5% to about 6%, about 4.5% to about 7%, about 4.5% to about 8%, about 4.5% to about 9%, about 4.5% to about 10%, about 4.5% to about 12%, about 4.5% to about 13.3%, about 4.7% to about 5%, about 4.7% to about 5.2%, about 4.7% to about 5.5%, about 4.7% to about 6%, about 4.7% to about 7%, about 4.7% to about 8%, about 4.7% to about 9%, about 4.7% to about 10%, about 4.7% to about 12%, about 4.7% to about 13.3%, about 5% to about 5.2%, about 5% to about 5.5%, about 5% to about 6%, about 5% to about 7%, about 5% to about 8%, about 5% to about 9%, about 5% to about 10%, about 5% to about 12%, about 5% to about 13.3%, about 5.2% to about 5.5%, about 5.2% to about 6%, about 5.2% to about 7%, about 5.2% to about 8%, about 5.2% to about 9%, about 5.2% to about 10%, about 5.2% to about 12%, about 5.2% to about 13.3%, about 5.5% to about 6%, about 5.5% to about 7%, about 5.5% to about 8%, about 5.5% to about 9%, about 5.5% to about 10%, about 5.5% to about 12%, about 5.5% to about 13.3%, about 6% to about 7%, about 6% to about 8%, about 6% to about 9%, about 6% to about 10%, about 6% to about 12%, about 6% to about 13.3%, about 7% to about 8%, about 7% to about 9%, about 7% to about 10%, about 7% to about 12%, about 7% to about 13.3%, about 8% to about 9%, about 8% to about 10%, about 8% to about 12%, about 8% to about 13.3%, about 9% to about 10%, about 9% to about 12%, about 9% to about 13.3%, about 10% to about 12%, about 10% to about 13.3%, or about 12% to about 13.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 4.5%, about4.7%, about 5%, about 5.2%, about 5.5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 12%, or about 13.3%.

[0275] In an aspect is provided a substituted or unsubstituted dehydrogenated polyethylene, wherein a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of repeating ethylene units of a polymer are olefinic.

[0276] In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at least 0.62%, at least 0.81%, at least 1.06%, at least 1.09%, at least 1.34%, at least 1.42%, at least 1.46%, at least 1.76%, at least 2.17%, at least 2.3%, at least 2.38%, at least 2.55%, at least 3.54%, or more. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at most 0.62%, at most 0.81%, at most 1.06%, at most 1.09%, at most 1.34%, at most 1.42%, at most 1.46%, at most 1.76%, at most 2.17%, at most 2.3%, at most 2.38%, at most 2.55%, at most 3.54%, or less.

[0277] In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 % to about 2.38 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at least about 0.1 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at most about 2.38 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 % to about 0.62 %, about 0.1 % to about 0.81 %, about 0.1 % to about 1.06 %, about 0.1 % to about 1.09 %, about 0.1 % to about 1.34 %, about 0.1 % to about 1.42 %, about 0.1 % to about 1.46 %, about 0.1 % to about 1.76 %, about 0.1 % to about 2.17 %, about 0.1 % to about 2.3 %, about 0.1 % to about 2.38 %, about 0.62 % to about 0.81 %, about 0.62 % to about 1.06 %, about 0.62 % to about 1.09 %, about 0.62 % to about 1.34 %, about 0.62 % to about 1.42 %, about 0.62 % to about 1.46 %, about 0.62 % to about 1.76 %, about 0.62 % to about 2.17 %, about 0.62 % to about 2.3 %, about 0.62 % to about 2.38 %, about 0.81 % to about 1.06 %, about 0.81 % to about 1.09 %, about 0.81 % to about 1.34 %, about 0.81 % to about 1.42 %, about 0.81 % to about 1.46 %, about 0.81 % to about 1.76 %, about 0.81 % to about 2.17 %, about 0.81 % to about 2.3 %, about 0.81 % to about 2.38 %, about 1.06 % to about 1.09 %, about 1.06 % to about 1.34 %, about 1.06 % to about 1.42 %, about 1.06 % to about 1.46 %, about 1.06 % to about 1.76 %, about 1.06 % to about 2.17 %, about 1.06 % to about 2.3 %, about 1.06 % to about 2.38 %, about 1.09 % to about 1.34 %, about 1.09 % to about 1.42 %, about 1.09 % to about 1.46%, about 1.09 % to about 1.76 %, about 1.09 % to about 2.17 %, about 1.09 % to about 2.3 %, about 1.09 % to about 2.38 %, about 1.34 % to about 1.42 %, about 1.34 % to about 1.46 %, about 1.34 % to about 1.76 %, about 1.34 % to about 2.17 %, about 1.34 % to about 2.3 %, about 1.34 % to about 2.38 %, about 1.42 % to about 1.46 %, about 1.42 % to about 1.76 %, about 1.42 % to about 2.17 %, about 1.42 % to about 2.3 %, about 1.42 % to about 2.38 %, about 1.46 % to about 1.76 %, about 1.46 % to about 2.17 %, about 1.46 % to about 2.3 %, about 1.46 % to about 2.38 %, about 1.76 % to about 2.17 %, about 1.76 % to about 2.3 %, about 1.76 % to about 2.38 %, about 2.17 % to about 2.3 %, about 2.17 % to about 2.38 %, or about 2.3 % to about 2.38 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 %, about 0.62 %, about 0.81 %, about 1.06 %, about 1.09 %, about 1.34 %, about 1.42 %, about 1.46 %, about 1.76 %, about 2.17 %, about 2.3 %, or about 2.38 %.

[0278] In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 % to about 10 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at least about 0.1 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at most about 10 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 % to about 0.62 %, about 0.1 % to about 0.81 %, about 0.1 % to about 1.34 %, about 0.1 % to about 1.09 %, about 0.1 % to about 1.34 %, about 0.1 % to about 1.76 %, about 0.1 % to about 2.38 %, about 0.1 % to about 2.55 %, about 0.1 % to about 3.54 %, about 0.1 % to about 4 %, about 0.1 % to about 10 %, about 0.62 % to about 0.81 %, about 0.62 % to about 1.34 %, about 0.62 % to about 1.09 %, about 0.62 % to about 1.34 %, about 0.62 % to about 1.76 %, about 0.62 % to about 2.38 %, about 0.62 % to about 2.55 %, about 0.62 % to about 3.54 %, about 0.62 % to about 4 %, about 0.62 % to about 10 %, about 0.81 % to about 1.34 %, about 0.81 % to about 1.09 %, about 0.81 % to about 1.34 %, about 0.81 % to about 1.76 %, about 0.81 % to about 2.38 %, about 0.81 % to about 2.55 %, about 0.81 % to about 3.54 %, about 0.81 % to about 4 %, about 0.81 % to about 10 %, about 1.34 % to about 1.09 %, about 1.34 % to about 1.34 %, about 1.34 % to about 1.76 %, about 1.34 % to about 2.38 %, about 1.34 % to about 2.55 %, about 1.34 % to about 3.54 %, about 1.34 % to about 4 %, about 1.34 % to about 10 %, about 1.09 % to about 1.34 %, about 1.09 % to about 1.76 %, about 1.09 % to about 2.38 %, about 1.09 % to about 2.55 %, about 1.09 % to about 3.54 %, about 1.09 % to about 4 %, about 1.09 % to about 10 %, about 1.34 % to about 1.76 %, about 1.34 % to about 2.38 %, about 1.34 % to about2.55 %, about 1.34 % to about 3.54 %, about 1.34 % to about 4 %, about 1.34 % to about 10 %, about 1.76 % to about 2.38 %, about 1.76 % to about 2.55 %, about 1.76 % to about 3.54 %, about 1.76 % to about 4 %, about 1.76 % to about 10 %, about 2.38 % to about 2.55 %, about 2.38 % to about 3.54 %, about 2.38 % to about 4 %, about 2.38 % to about 10 %, about 2.55 % to about 3.54 %, about 2.55 % to about 4 %, about 2.55 % to about 10 %, about 3.54 % to about 4 %, about 3.54 % to about 10 %, or about 4 % to about 10 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 %, about 0.62 %, about 0.81 %, about 1.34 %, about 1.09 %, about 1.34 %, about 1.76 %, about 2.38 %, about 2.55 %, about 3.54 %, about 4 %, or about 10 %.

[0279] In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 % to about 20 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at least about 0.1 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at most about 20 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 % to about 1 %, about 0.1 % to about 1.5 %, about 0.1 % to about 1.75 %, about 0.1 % to about 2 %, about 0.1 % to about 2.5 %, about 0.1 % to about 3 %, about 0.1 % to about 4 %, about 0.1 % to about 5 %, about 0.1 % to about 7.5 %, about 0.1 % to about 10 %, about 0.1 % to about 20 %, about 1 % to about 1.5 %, about 1 % to about 1.75 %, about 1 % to about 2 %, about 1 % to about 2.5 %, about 1 % to about 3 %, about 1 % to about 4 %, about 1 % to about 5 %, about 1 % to about 7.5 %, about 1 % to about 10 %, about 1 % to about 20 %, about 1.5 % to about 1.75 %, about 1.5 % to about 2 %, about 1.5 % to about 2.5 %, about 1.5 % to about 3 %, about 1.5 % to about 4 %, about 1.5 % to about 5 %, about 1.5 % to about 7.5 %, about 1.5 % to about 10 %, about 1.5 % to about 20 %, about 1.75 % to about 2 %, about 1.75 % to about 2.5 %, about 1.75 % to about 3 %, about 1.75 % to about 4 %, about 1.75 % to about 5 %, about 1.75 % to about 7.5 %, about 1.75 % to about 10 %, about 1.75 % to about 20 %, about 2 % to about 2.5 %, about 2 % to about 3 %, about 2 % to about 4 %, about 2 % to about 5 %, about 2 % to about 7.5 %, about 2 % to about 10 %, about 2 % to about 20 %, about 2.5 % to about 3 %, about 2.5 % to about 4 %, about 2.5 % to about 5 %, about 2.5 % to about 7.5 %, about 2.5 % to about 10 %, about 2.5 % to about 20 %, about 3 % to about 4 %, about 3 % to about 5 %, about 3 % to about 7.5 %, about 3 % to about 10 %, about 3 % to about 20 %, about 4 % to about 5 %, about 4 % to about 7.5 %, about 4 % to about 10 %, about 4 % to about 20 %, about 5 % to about 7.5 %,about 5 % to about 10 %, about 5 % to about 20 %, about 7.5 % to about 10 %, about 7.5 % to about 20 %, or about 10 % to about 20 %.

[0280] In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 %, about 1 %, about 1.5 %, about 1.75 %, about 2 %, about 2.5 %, about 3 %, about 4 %, about 5 %, about 7.5 %, about 10 %, or about 20 %.

[0281] In embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at least about 0.01%, at least about 0.05%, at least about 0.1%, at least about 0.15%, at least about 0.17%, at least about 0.19%, at least about 0.2%, at least about 0.22%, at least about 0.25%, at least about 0.3%, at least about 0.35%, at least about 0.38%, at least about 0.4%, at least about 0.45%, at least about 0.5%, at least about 0.52%, at least about 0.55%, at least about 0.56, at least about 0.6%, at least about 0.65%, at least about 0.75%, at least about 1%, at least about 2%, at least about 3%, at least about 4%, at least about 5%, at least about 10%, or more.

[0282] In embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at most about 0.01%, at most about 0.05%, at most about 0.1%, at most about 0.15%, at most about 0.17%, at most about 0.19%, at most about 0.2%, at most about 0.22%, at most about 0.25%, at most about 0.3%, at most about 0.35%, at most about 0.38%, at most about 0.4%, at most about 0.45%, at most about 0.5%, at most about 0.52%, at most about 0.55%, at most about 0.56, at most about 0.6%, at most about 0.65%, at most about 0.75%, at most about 1%, at most about 2%, at most about 3%, at most about 4%, at most about 5%, at most about 10%, or less.

[0283] In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.01 % to about 10 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at least about 0.01 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at most about 10 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.01 % to about 0.05 %, about 0.01 % to about 0.1 %, about 0.01 % to about 0.19 %, about 0.01 % to about 0.22 %, about 0.01 % to about 0.25 %, about 0.01 % to about 0.38 %, about 0.01 % to about 0.52 %, about 0.01 % to about 0.56 %, about 0.01 % to about 1 %, about 0.01 % to about 2 %, about 0.01 % to about 10 %, about 0.05 % to about 0.1 %, about 0.05 % to about 0.19 %, about 0.05 % to about 0.22 %, about 0.05 % to about 0.25 %, about 0.05 % to about 0.38 %, about 0.05 % to about 0.52 %, about 0.05 % to about 0.56 %, about 0.05 % to about 1 %, about0.05 % to about 2 %, about 0.05 % to about 10 %, about 0.1 % to about 0.19 %, about 0.1 % to about 0.22 %, about 0.1 % to about 0.25 %, about 0.1 % to about 0.38 %, about 0.1 % to about 0.52 %, about 0.1 % to about 0.56 %, about 0.1 % to about 1 %, about 0.1 % to about 2 %, about 0.1 % to about 10 %, about 0.19 % to about 0.22 %, about 0.19 % to about 0.25 %, about 0.19 % to about 0.38 %, about 0.19 % to about 0.52 %, about 0.19 % to about 0.56 %, about 0.19 % to about 1 %, about 0.19 % to about 2 %, about 0.19 % to about 10 %, about 0.22 % to about 0.25 %, about 0.22 % to about 0.38 %, about 0.22 % to about 0.52 %, about 0.22 % to about 0.56 %, about 0.22 % to about 1 %, about 0.22 % to about 2 %, about 0.22 % to about 10 %, about 0.25 % to about 0.38 %, about 0.25 % to about 0.52 %, about 0.25 % to about 0.56 %, about 0.25 % to about 1 %, about 0.25 % to about 2 %, about 0.25 % to about 10 %, about 0.38 % to about 0.52 %, about 0.38 % to about 0.56 %, about 0.38 % to about 1 %, about 0.38 % to about 2 %, about 0.38 % to about 10 %, about 0.52 % to about 0.56 %, about 0.52 % to about 1 %, about 0.52 % to about 2 %, about 0.52 % to about 10 %, about 0.56 % to about 1 %, about 0.56 % to about 2 %, about 0.56 % to about 10 %, about 1 % to about 2 %, about 1 % to about 10 %, or about 2 % to about 10 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.01 %, about 0.05 %, about 0.1 %, about 0.19 %, about 0.22 %, about 0.25 %, about 0.38 %, about 0.52 %, about 0.56 %, about 1 %, about 2 %, or about 10 %.

[0284] In an aspect is provided a substituted or unsubstituted dehydrogenated polyethylene, having a number average molecular weight of 2,200 Da or greater.

[0285] In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 500,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 400,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 300,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 200,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 100,000 Da. In embodiments, the substituted or unsubstituted dehydrogenatedpolyethylene has a number average molecular weight of from about 1,000 Da to about 50,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 40,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 30,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 20,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 10,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 500,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 400,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 300,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 200,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 100,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 50,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 40,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 30,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 20,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 10,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 6,500 Da or a number average molecular weight greater than about 6,700 Da.

[0286] In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 500,000 Da. In embodiments, thesubstituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 400,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 300,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 200,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 100,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 50,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 40,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 30,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 20,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 10,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 500,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 400,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 300,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 200,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 100,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 50,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 40,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 30,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 20,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecularweight of from 2,200 Da to 10,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 6,500 Da or a number average molecular weight greater than 6,700 Da.

[0287] In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at least about 0.5 kDa, at least about 1 kDa, at least about 2 kDa, at least about 4 kDa, at least about 5 kDa, at least about 5.22 kDa, at least about 6 kDa, at least about 7 kDa, at least about 8 kDa, at least about 9 kDa, at least about 10 kDa, at least about 11 kDa, at least about 12 kDa, at least about 13 kDa, at least about 14 kDa, at least about 15 kDa, at least about 16 kDa, at least about 17 kDa, at least about 18 kDa, at least about 18.2 kDa, at least about 19 kDa, at least about 20 kDa, at least about 21 kDa, at least about 25 kDa, at least about 30 kDa, at least about 35 kDa, at least about 40 kDa, at least about 45 kDa, or at least about 50 kDa, or more.

[0288] Alteratively, or in addition, in embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at most about 0.5 kDa, at most about 1 kDa, at most about 2 kDa, at most about 4 kDa, at most about 5 kDa, at most about 5.22 kDa, at most about 6 kDa, at most about 7 kDa, at most about 8 kDa, at most about 9 kDa, at most about 10 kDa, at most about 11 kDa, at most about 12 kDa, at most about 13 kDa, at most about 14 kDa, at most about 15 kDa, at most about 16 kDa, at most about 17 kDa, at most about 18 kDa, at most about 18.2 kDa, at most about 19 kDa, at most about 20 kDa, at most about 21 kDa, at most about 25 kDa, at most about 30 kDa, at most about 35 kDa, at most about 40 kDa, at most about 45 kDa, at most about 50 kDa, or less.

[0289] In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at most about 5.22 kDa, or at least about 18.2 kDa, more more. In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at least about 5.22 kDa, or at least about 18.2 kDa, or less.

[0290] In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is about 2 kDa to about 50 kDa. In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at least about 2 kDa. In embodiments, the number average molecular weight ofthe substituted or unsubstituted dehydrogenated polyethylene is at most about 50 kDa. In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is about 2 kDa to about 4 kDa, about 2 kDa to about 5 kDa, about 2 kDa to about 5.22 kDa, about 2 kDa to about 8 kDa, about 2 kDa to about 10 kDa, about 2 kDa to about 12 kDa, about 2 kDa to about 15 kDa, about 2 kDa to about 18.2 kDa, about 2 kDa to about 20 kDa, about 2 kDa to about 35 kDa, about 2 kDa to about 50 kDa, about 4 kDa to about 5 kDa, about 4 kDa to about 5.22 kDa, about 4 kDa to about 8 kDa, about 4 kDa to about 10 kDa, about 4 kDa to about 12 kDa, about 4 kDa to about 15 kDa, about 4 kDa to about 18.2 kDa, about 4 kDa to about 20 kDa, about 4 kDa to about 35 kDa, about 4 kDa to about 50 kDa, about 5 kDa to about 5.22 kDa, about 5 kDa to about 8 kDa, about 5 kDa to about 10 kDa, about 5 kDa to about 12 kDa, about 5 kDa to about 15 kDa, about 5 kDa to about 18.2 kDa, about 5 kDa to about 20 kDa, about 5 kDa to about 35 kDa, about 5 kDa to about 50 kDa, about 5.22 kDa to about 8 kDa, about 5.22 kDa to about 10 kDa, about 5.22 kDa to about 12 kDa, about 5.22 kDa to about 15 kDa, about 5.22 kDa to about 18.2 kDa, about 5.22 kDa to about 20 kDa, about 5.22 kDa to about 35 kDa, about 5.22 kDa to about 50 kDa, about 8 kDa to about 10 kDa, about 8 kDa to about 12 kDa, about 8 kDa to about 15 kDa, about 8 kDa to about 18.2 kDa, about 8 kDa to about 20 kDa, about 8 kDa to about 35 kDa, about 8 kDa to about 50 kDa, about 10 kDa to about 12 kDa, about 10 kDa to about 15 kDa, about 10 kDa to about 18.2 kDa, about 10 kDa to about 20 kDa, about 10 kDa to about 35 kDa, about 10 kDa to about 50 kDa, about 12 kDa to about 15 kDa, about 12 kDa to about 18.2 kDa, about 12 kDa to about 20 kDa, about 12 kDa to about 35 kDa, about 12 kDa to about 50 kDa, about 15 kDa to about 18.2 kDa, about 15 kDa to about 20 kDa, about 15 kDa to about 35 kDa, about 15 kDa to about 50 kDa, about 18.2 kDa to about 20 kDa, about 18.2 kDa to about 35 kDa, about 18.2 kDa to about 50 kDa, about 20 kDa to about 35 kDa, about 20 kDa to about 50 kDa, or about 35 kDa to about 50 kDa. In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is about 2 kDa, about 4 kDa, about 5 kDa, about 5.22 kDa, about 8 kDa, about 10 kDa, about 12 kDa, about 15 kDa, about 18.2 kDa, about 20 kDa, about 35 kDa, or about 50 kDa.

[0291] In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at least about 0.5 kDa, at least about 1 kDa, at least about 1.23 kDa, at least about 1.67 kDa, at least about 2 kDa, at least about 2.24 kDa, at leastabout 3 kDa, at least about 3.9 kDa, at least about 4 kDa, at least about 4.07 kDa, at least about 5 kDa, at least about 5.22 kDa, at least about 6 kDa, at least about 7 kDa, at least about 8 kDa, at least about 9 kDa, at least about 10 kDa, at least about 11 kDa, at least about 12 kDa, at least about 13 kDa, at least about 14 kDa, at least about 15 kDa, at least about 16 kDa, at least about 17 kDa, at least about 18 kDa, at least about 18.2 kDa, at least about 19 kDa, at least about 20 kDa, at least about 21 kDa, at least about 25 kDa, at least about 30 kDa, at least about 35 kDa, at least about 40 kDa, at least about 45 kDa, or at least about 50 kDa, or at least about 100 kDa, or at least about 200 kDa, or more.

[0292] Alteratively, or in addition, in embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at most about 0.5 kDa, at most about 1 kDa, at most about 1.23 kDa, at most about 1.67 kDa, at most about 2 kDa, at most about 2.24 kDa, at most about 3 kDa, at most about 3.9 kDa, at most about 4 kDa, at most about 4.07 kDa, at most about 5 kDa, at most about 5.22 kDa, at most about 6 kDa, at most about 7 kDa, at most about 8 kDa, at most about 9 kDa, at most about 10 kDa, at most about 11 kDa, at most about 12 kDa, at most about 13 kDa, at most about 14 kDa, at most about 15 kDa, at most about 16 kDa, at most about 17 kDa, at most about 18 kDa, at most about 18.2 kDa, at most about 19 kDa, at most about 20 kDa, at most about 21 kDa, at most about 25 kDa, at most about 30 kDa, at most about 35 kDa, at most about 40 kDa, at most about 45 kDa, or at most about 50 kDa, or at most about 100 kDa, or at most about 200 kDa, or less.

[0293] In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is about 0.5 kDa to about 50 kDa. In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at least about 0.5 kDa. In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at most about 50 kDa. In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is about 0.5 kDa to about 1 kDa, about 0.5 kDa to about 1.23 kDa, about 0.5 kDa to about 1.67 kDa, about 0.5 kDa to about 2 kDa, about 0.5 kDa to about 2.24 kDa, about 0.5 kDa to about 3 kDa, about 0.5 kDa to about 3.9 kDa, about 0.5 kDa to about 4.07 kDa, about 0.5 kDa to about 5.22 kDa, about 0.5 kDa to about 10 kDa, about 0.5 kDa to about 50 kDa, about 1 kDa to about 1.23 kDa, about 1 kDa to about 1.67 kDa, about 1 kDa to about 2kDa, about 1 kDa to about 2.24 kDa, about 1 kDa to about 3 kDa, about 1 kDa to about 3.9 kDa, about 1 kDa to about 4.07 kDa, about 1 kDa to about 5.22 kDa, about 1 kDa to about 10 kDa, about 1 kDa to about 50 kDa, about 1.23 kDa to about 1.67 kDa, about 1.23 kDa to about 2 kDa, about 1.23 kDa to about 2.24 kDa, about 1.23 kDa to about 3 kDa, about 1.23 kDa to about 3.9 kDa, about 1.23 kDa to about 4.07 kDa, about 1.23 kDa to about 5.22 kDa, about 1.23 kDa to about 10 kDa, about 1.23 kDa to about 50 kDa, about 1.67 kDa to about 2 kDa, about 1.67 kDa to about 2.24 kDa, about 1.67 kDa to about 3 kDa, about 1.67 kDa to about 3.9 kDa, about 1.67 kDa to about 4.07 kDa, about 1.67 kDa to about 5.22 kDa, about 1.67 kDa to about 10 kDa, about 1.67 kDa to about 50 kDa, about 2 kDa to about 2.24 kDa, about 2 kDa to about 3 kDa, about 2 kDa to about 3.9 kDa, about 2 kDa to about 4.07 kDa, about 2 kDa to about 5.22 kDa, about 2 kDa to about 10 kDa, about 2 kDa to about 50 kDa, about 2.24 kDa to about 3 kDa, about 2.24 kDa to about 3.9 kDa, about 2.24 kDa to about 4.07 kDa, about 2.24 kDa to about 5.22 kDa, about 2.24 kDa to about 10 kDa, about 2.24 kDa to about 50 kDa, about 3 kDa to about 3.9 kDa, about 3 kDa to about 4.07 kDa, about 3 kDa to about 5.22 kDa, about 3 kDa to about 10 kDa, about 3 kDa to about 50 kDa, about 3.9 kDa to about 4.07 kDa, about 3.9 kDa to about 5.22 kDa, about 3.9 kDa to about 10 kDa, about 3.9 kDa to about 50 kDa, about 4.07 kDa to about 5.22 kDa, about 4.07 kDa to about 10 kDa, about 4.07 kDa to about 50 kDa, about 5.22 kDa to about 10 kDa, about 5.22 kDa to about 50 kDa, or about 10 kDa to about 50 kDa. In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is about 0.5 kDa, about 1 kDa, about 1.23 kDa, about 1.67 kDa, about 2 kDa, about 2.24 kDa, about 3 kDa, about 3.9 kDa, about 4.07 kDa, about 5.22 kDa, about 10 kDa, or about 50 kDa.

[0294] In embodiments, the polydispersity of the dehydrogenated polyethylene is at least about 1.001, at least about 1.01, at least about 1.05, at least about 1.1, at least about 1.25, at least about 1.5, at least about 1.6, at least about 1.7, at least about 1.75, at least about 1.8, at least about 1.84, at least about 1.9, at least about 2, at least about 2.1, at least about 2.25, at least about 2.5, at least about 2.75, at least about 3, at least about 3.25, at least about 3.35, at least about 3.4, at least about 3.45, at least about 3.48, at least about 3.5, at least about 3.55, at least about 3.75, at least about 4, at least about 4.25, at least about 4.5, at least about 4.75, at least about 5, or more.

[0295] In embodiments, the polydispersity of the dehydrogenated polyethylene is at most about 1.001, at most about 1.01, at most about 1.05, at most about 1.1, at most about 1.25, at most about 1.5, at most about 1.6, at most about 1.7, at most about 1.75, at most about 1.8, at most about 1.84, at most about 1.9, at most about 2, at most about 2.1, at most about 2.25, at most about 2.5, at most about 2.75, at most about 3, at most about 3.25, at most about 3.35, at most about 3.4, at most about 3.45, at most about 3.48, at most about 3.5, at most about 3.55, at most about 3.75, at most about 4, at most about 4.25, at most about 4.5, at most about 4.75, at most about 5, or less.

[0296] In embodiments, the polydispersity of the dehydrogenated polyethylene is about 1.1 to about 8. In embodiments, the polydispersity of the dehydrogenated polyethylene is at least about 1.1. In embodiments, the polydispersity of the dehydrogenated polyethylene is at most about 8. In embodiments, the polydispersity of the dehydrogenated polyethylene is about 1.1 to about 1.3, about 1.1 to about 1.5, about 1.1 to about 1.7, about 1.1 to about 1.8, about 1.1 to about 1.84, about 1.1 to about 1.9, about 1.1 to about 2.5, about 1.1 to about 3.25, about 1.1 to about 3.48, about 1.1 to about 5, about 1.1 to about 8, about 1.3 to about 1.5, about 1.3 to about 1.7, about 1.3 to about 1.8, about 1.3 to about 1.84, about 1.3 to about 1.9, about 1.3 to about 2.5, about 1.3 to about 3.25, about 1.3 to about 3.48, about 1.3 to about 5, about 1.3 to about 8, about 1.5 to about 1.7, about 1.5 to about 1.8, about 1.5 to about 1.84, about 1.5 to about 1.9, about 1.5 to about 2.5, about 1.5 to about 3.25, about 1.5 to about 3.48, about 1.5 to about 5, about 1.5 to about 8, about 1.7 to about 1.8, about 1.7 to about 1.84, about 1.7 to about 1.9, about 1.7 to about 2.5, about 1.7 to about 3.25, about 1.7 to about 3.48, about 1.7 to about 5, about 1.7 to about 8, about 1.8 to about 1.84, about 1.8 to about 1.9, about 1.8 to about 2.5, about 1.8 to about 3.25, about 1.8 to about 3.48, about 1.8 to about 5, about 1.8 to about 8, about 1.84 to about 1.9, about 1.84 to about 2.5, about 1.84 to about 3.25, about 1.84 to about 3.48, about 1.84 to about 5, about 1.84 to about 8, about 1.9 to about 2.5, about 1.9 to about 3.25, about 1.9 to about 3.48, about 1.9 to about 5, about 1.9 to about 8, about 2.5 to about 3.25, about 2.5 to about 3.48, about 2.5 to about 5, about 2.5 to about 8, about 3.25 to about 3.48, about 3.25 to about 5, about 3.25 to about 8, about 3.48 to about 5, about 3.48 to about 8, or about 5 to about 8. In embodiments, the polydispersity of the dehydrogenated polyethylene is about 1.1, about 1.3, about 1.5, about 1.7, about 1.8, about 1.84, about 1.9, about 2.5, about 3.25, about 3.48, about 5, or about 8.

[0297] In embodiments, a percentage of from about 0.01% to about 11% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 0.01% to about 10% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 0.01% to about 9% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 0.01% to about 8% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of about 8% or less of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 0.01% to about 1.5% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 2.4% to about 4.3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 4.5% to about 13.2% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 1% to about 3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 1.5% to about 3% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of about 1.9% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 1.7% to about 2.3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 1.7% to about 2.1% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 1.9% to about 2.1% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of about 1.7% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of about 1.8% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of about 1.9% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of about 2% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments,a percentage of about 2.1% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of about 2.2% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of about 2.3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.

[0298] In embodiments, a percentage of from 0.01% to 11% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 0.01% to 10% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 0.01% to 9% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 0.01% to 8% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 8% or less of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 0.01% to 1.5% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 2.4% to 4.3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 4.5% to 13.2% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 1% to 3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 1.5% to 3% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 1.9% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 1.7% to 2.3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 1.7% to 2.1% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 1.9% to 2.1% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 1.7% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 1.8% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene areunsaturated. In embodiments, a percentage of 1.9% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 2% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 2.1% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 2.2% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 2.3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.

[0299] In some embodiments, the percentage of aromatic carbons in the dehydrogenated polyethylene is at least about 0%, at least about 0.0001%, at least about 0.001%, at least about 0.01%, at least about 0.02%, at least about 0.03%, at least about 0.04%, at least about 0.05%, at least about 0.06%, at least about 0.07%, at least about 0.08%, at least about 0.09, at least about 0.1%, at least about 0.11%, at least about 0.12%, at least about 0.13%, at least about 0.14%, at least about 0.15%, at least about 0.16%, at least about 0.17%, at least about 0.18%, at least about 0.19%, at least about 0.2%, at least about 0.22%, at least about 0.24%, at least about 0.26%, at least about 0.28%, at least about 0.3%, at least about 0.32%, at least about 0.33%, at least about 0.34%, at least about 0.35%, at least about 0.4%, at least about 0.5%, at least about 0.54%, at least about 0.55%, at least about 0.6%, at least about 0.7%, at least about 0.75%, at least about 0.77%, at least about 0.8%, at least about 0.9%, at least about 1%, at least about 1.1%, at least about 1.2%, at least about 1.23%, at least about 1.3%, at least about 1.39%, at least about 1.4%, at least about 1.43%, at least about 1.47%, at least about 1.5%, at least about 1.75%, at least about 2%, at least about 3%, at least about 4%, at least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, at least about 10%, at least about 12.5%, at least about 15%, at least about 17.5%, at least about 20%, at least about 50%, at least about 75%, or more.

[0300] In some embodiments, the percentage of aromatic carbons in the dehydrogenated polyethylene is at most about 0%, at most about 0.0001%, at most about 0.001%, at most about 0.01%, at most about 0.02%, at most about 0.03%, at most about 0.04%, at most about 0.05%, at most about 0.06%, at most about 0.07%, at most about 0.08%, at most about 0.09, at most about 0.1%, at most about 0.11%, at most about 0.12%, at most about 0.13%, at most about 0.14%, atmost about 0.15%, at most about 0.16%, at most about 0.17%, at most about 0.18%, at most about 0.19%, at most about 0.2%, at most about 0.22%, at most about 0.24%, at most about 0.26%, at most about 0.28%, at most about 0.3%, at most about 0.32%, at most about 0.33%, at most about 0.34%, at most about 0.35%, at most about 0.4%, at most about 0.5%, at most about 0.54%, at most about 0.55%, at most about 0.6%, at most about 0.7%, at most about 0.75%, at most about 0.77%, at most about 0.8%, at most about 0.9%, at most about 1%, at most about 1.1%, at most about 1.2%, at most about 1.23%, at most about 1.3%, at most about 1.39%, at most about 1.4%, at most about 1.43%, at most about 1.47%, at most about 1.5%, at most about 1.75%, at most about 2%, at most about 3%, at most about 4%, at most about 5%, at most about 6%, at most about 7%, at most about 8%, at most about 9%, at most about 10%, at most about 12.5%, at most about 15%, at most about 17.5%, at most about 20%, at most about 50%, at most about 75%, or more.

[0301] In some embodiments, the percentage of aromatic carbons in the dehydrogenated polyethylene is about 0.001 % to about 10 %. In some embodiments, the percentage of aromatic carbons in the dehydrogenated polyethylene is at least about 0.001 %. In some embodiments, the percentage of aromatic carbons in the dehydrogenated polyethylene is at most about 10 %. In some embodiments, the percentage of aromatic carbons in the dehydrogenated polyethylene is about 0.001 % to about 0.01 %, about 0.001 % to about 0.02 %, about 0.001 % to about 0.04 %, about 0.001 % to about 0.08 %, about 0.001 % to about 0.09 %, about 0.001 % to about 0.1 %, about 0.001 % to about 0.11 %, about 0.001 % to about 0.33 %, about 0.001 % to about 0.47 %, about 0.001 % to about 1.47 %, about 0.001 % to about 10 %, about 0.01 % to about 0.02 %, about 0.01 % to about 0.04 %, about 0.01 % to about 0.08 %, about 0.01 % to about 0.09 %, about 0.01 % to about 0.1 %, about 0.01 % to about 0.11 %, about 0.01 % to about 0.33 %, about 0.01 % to about 0.47 %, about 0.01 % to about 1.47 %, about 0.01 % to about 10 %, about 0.02 % to about 0.04 %, about 0.02 % to about 0.08 %, about 0.02 % to about 0.09 %, about 0.02 % to about 0.1 %, about 0.02 % to about 0.11 %, about 0.02 % to about 0.33 %, about 0.02 % to about 0.47 %, about 0.02 % to about 1.47 %, about 0.02 % to about 10 %, about 0.04 % to about 0.08 %, about 0.04 % to about 0.09 %, about 0.04 % to about 0.1 %, about 0.04 % to about 0.11 %, about 0.04 % to about 0.33 %, about 0.04 % to about 0.47 %, about 0.04 % to about 1.47 %, about 0.04 % to about 10 %, about 0.08 % to about 0.09 %, about 0.08 % to about 0.1 %, about 0.08 % to about 0.11 %, about 0.08 % to about 0.33 %, about 0.08 % to about 0.47 %, about 0.08% to about 1.47 %, about 0.08 % to about 10 %, about 0.09 % to about 0.1 %, about 0.09 % to about 0.11 %, about 0.09 % to about 0.33 %, about 0.09 % to about 0.47 %, about 0.09 % to about 1.47 %, about 0.09 % to about 10 %, about 0.1 % to about 0.11 %, about 0.1 % to about 0.33 %, about 0.1 % to about 0.47 %, about 0.1 % to about 1.47 %, about 0.1 % to about 10 %, about 0.11 % to about 0.33 %, about 0.11 % to about 0.47 %, about 0.11 % to about 1.47 %, about 0.11 % to about 10 %, about 0.33 % to about 0.47 %, about 0.33 % to about 1.47 %, about 0.33 % to about 10 %, about 0.47 % to about 1.47 %, about 0.47 % to about 10 %, or about 1.47 % to about 10 %. In some embodiments, the percentage of aromatic carbons in the dehydrogenated polyethylene is about 0.001 %, about 0.01 %, about 0.02 %, about 0.04 %, about 0.08 %, about 0.09 %, about 0.1 %, about 0.11 %, about 0.33 %, about 0.47 %, about 1.47 %, or about 10 %.

[0302] In embodiments, the distribution of unsaturated monomer units in the substituted or unsubstituted dehydrogenated polyethylene is irregular.

[0303] In embodiments, the dehydrogenated polyethylene is produced from an HDPE precursor. In embodiments, the HDPE precursor has a number average molecular weight of at least about 0.5 kDa, at least about 1 kDa, at least about 2 kDa, at least about 5 kDa, at least about 10 kDa, at least about 15 kDa, at least about 20 kDa, at least about 22.5 kDa, at least about 25 kDa, at least about 26.1 kDa, at least about 37.5 kDa, at least about 30 kDa, at least about 32.5 kDa, at least about 35 kDa, at least about 37.5 kDa, at least about 40 kDa, at least about 42.5 kDa, at least about 45 kDa, at least about 50 kDa, at least about 55 kDa, at least about 60 kDa, at least about 65 kDa, at least about 75 kDa, at least about 90 kDa, at least about 100 kDa, or more.

[0304] In embodiments, the HDPE precursor has a number average molecular weight of at most about 0.5 kDa, at most about 1 kDa, at most about 2 kDa, at most about 5 kDa, at most about 10 kDa, at most about 15 kDa, at most about 20 kDa, at most about 22.5 kDa, at most about 25 kDa, at most about 26.1 kDa, at most about 37.5 kDa, at most about 30 kDa, at most about 32.5 kDa, at most about 35 kDa, at most about 37.5 kDa, at most about 40 kDa, at most about 42.5 kDa, at most about 45 kDa, at most about 50 kDa, at most about 55 kDa, at most about 60 kDa, at most about 65 kDa, at most about 75 kDa, at most about 90 kDa, at most about 100 kDa, or less.

[0305] In embodiments, the number average molecular weight of the HDPE precursor is about 0.5 kDa to about 100 kDa. In embodiments, the number average molecular weight of the HDPE precursor is at least about 0.5 kDa. In embodiments, the number average molecular weight of the HDPE precursor is at most about 100 kDa. In embodiments, the number average molecular weight of the HDPE precursor is about 0.5 kDa to about 1 kDa, about 0.5 kDa to about 5 kDa, about 0.5 kDa to about 10 kDa, about 0.5 kDa to about 15 kDa, about 0.5 kDa to about 20 kDa, about 0.5 kDa to about 25 kDa, about 0.5 kDa to about 26.1 kDa, about 0.5 kDa to about 30 kDa, about 0.5 kDa to about 35 kDa, about 0.5 kDa to about 50 kDa, about 0.5 kDa to about 100 kDa, about 1 kDa to about 5 kDa, about 1 kDa to about 10 kDa, about 1 kDa to about 15 kDa, about 1 kDa to about 20 kDa, about 1 kDa to about 25 kDa, about 1 kDa to about 26.1 kDa, about 1 kDa to about 30 kDa, about 1 kDa to about 35 kDa, about 1 kDa to about 50 kDa, about 1 kDa to about 100 kDa, about 5 kDa to about 10 kD...

Claims

WHAT IS CLAIMED IS:

1. A method of degrading a substance, said method comprising: (iv) conducting one or more reaction(s) to form one or more olefin units in the substance; (v) subjecting, after step (i), to conditions for olefin metathesis; and (vi) subjecting, after step (i), to conditions for olefin isomerization.

2. The method of claim 1, wherein step (i) comprises subjecting the substance to conditions for dehydrogenation.

3. A method of making a substituted or unsubstituted alkene, said method comprising subjecting a dehydrogenated polymer to conditions for metathesis and to conditions for olefin isomerization.

4. A method of making a substituted or unsubstituted alkene, said method comprising subjecting a first substance to conditions for olefin metathesis and to conditions for olefin isomerization; wherein: (iii) said first substance comprises at least 20 carbon atoms per molecule; or (iv) prior to subjecting said first substance to conditions for olefin metathesis and to conditions for olefin isomerization, the method comprises subjecting a second substance to conditions for dehydrogenation, thereby forming said first substance.

5. The method of claim 4, wherein the substituted or unsubstituted alkene is a substituted or unsubstituted propene.

6. The method of claims 4, wherein said first substance is a substituted or unsubstituted dehydrogenated polyethylene.

7. A method of making an alkene, said method comprising mixing a dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s); wherein: (iii) the dehydrogenated polymer comprises at least 20 carbon atoms; or(iv) prior to said mixing, the method comprises mixing a polymer with one or more dehydrogenating reagent(s), thereby forming said dehydrogenated polymer.

8. A method of making a dehydrogenated polymer, said method comprising mixing a polymer with one or more dehydrogenating reagent(s), wherein (v) a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or 4.5% to 13.2% of monomer units in the dehydrogenated polymer are unsaturated; (vi) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da or greater; (vii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da and a percentage of from 0.01% to 10% of monomer units are unsaturated; or (viii) the dehydrogenated polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated.

9. The method of claim 8, wherein the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 6,500 Da or from about 6,700 Da to about 15,000 Da.

10. The method of claim 8, wherein the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 6,500 Da.

11. The method of claim 8, further comprising mixing the dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s), thereby forming an alkene.

12. The method of claim 7, wherein the dehydrogenated polymer is a substituted or unsubstituted dehydrogenated polyethylene.

13. The method of claim 7, wherein the alkene is a substituted or unsubstituted propene.

14. The method of claim 7, wherein the dehydrogenated polymer, the one or more olefin metathesis reagent(s), and the one or more isomerization reagent(s) are mixed simultaneously.

15. The method of claim 7, wherein the dehydrogenated polymer and the one or more olefin metathesis reagent(s) are mixed prior to adding the one or more isomerization reagent(s).

16. The method of claim 15, wherein the dehydrogenated polymer and one or more additional olefin metathesis reagent(s) are mixed prior to adding the one or more olefin metathesis reagent(s) and the one or more isomerization reagent(s).

17. The method of claim 7, wherein the one or more olefin metathesis reagent(s) comprises an ethenolysis catalyst.

18. The method of claim 7, wherein the one or more olefin metathesis reagent(s) comprises one or more homogeneous olefin metathesis catalyst(s) or one or more heterogeneous olefin metathesis catalyst(s).

19. The method of claim 18, wherein the one or more olefin metathesis reagent(s) further comprises ethylene.

20. The method of claim 18, wherein the homogeneous olefin metathesis catalyst is.

21. The method of claim 19, wherein the homogeneous olefin metathesis catalyst is.

22. The method of claim 18, wherein the heterogeneous olefin metathesis catalyst is Re2O7 / Al2O3or WO3 / Al2O3.

23. The method of claim 7, wherein the one or more isomerization reagent(s) comprises one or more homogeneous isomerization catalyst(s) or one or more heterogeneous isomerization catalyst(s).

24. The method of claim 23, wherein the one or more homogeneous isomerization catalyst(s) is selected from: , , , and .

25. The method of claim 23, wherein the one or more homogeneous isomerization catalyst(s) is.

26. The method of claim 23, wherein the one or more heterogeneous isomerization catalyst(s) is selected from: Na / Al2O3, K / Al2O3, Mg / Al2O3, MgO, NaO2, and KO2.

27. The method of claim 7, wherein the substituted or unsubstituted polymer is a high-density polyethylene, a low-density polyethylene, or a linear low-density polyethylene, or a co-polymer thereof.

28. The method of claim 7, wherein the one or more dehydrogenating reagent(s) comprises a transfer dehydrogenation catalyst.

29. The method of claim 7, wherein the one or more dehydrogenating reagent(s) comprises a hydrogen acceptor.

30. The method of claim 29, wherein the hydrogen acceptor comprises a C-C bond, a C=C bond, a C≡C bond, an N-N bond, an N=N bond, an N≡N bond, an O-O bond, an O=O bond, a C-N bond, a C=N bond, a C≡N bond, a C-O bond, a C=O bond, a C≡O bond, an S- S bond, a C-S bond, or a C=S bond.

31. The method of claim 29, wherein the hydrogen acceptor comprises a C=C bond.

32. The method of claim 29, wherein the hydrogen acceptor is ethylene, propylene, butene, tert-butylethylene, norbornene, norbornadiene, butadiene, styrene, acetylene, O2, CO2, CO, substituted or unsubstituted benzoquinone, or N2.

33. The method of claim 7, wherein the one or more dehydrogenating reagent(s) comprises a heterogeneous dehydrogenating catalyst.

34. The method of claim 33, wherein the heterogeneous dehydrogenating catalyst comprises a plurality of metallic elements.

35. The method of claim 33, wherein the heterogeneous dehydrogenating catalyst is a bimetallic catalyst.

36. The method of claim 33, wherein the heterogeneous dehydrogenating catalyst is a Pt / Sn catalyst or a Pt / Zn catalyst.

37. The method of claim 33, wherein the heterogeneous dehydrogenating catalyst is Pt / Sn-Al2O3 or Pt / Zn-SiO2.

38. The method of claim 7, wherein the one or more dehydrogenating reagent(s) comprises a homogeneous dehydrogenating catalyst.

39. The method of claim 38, wherein the homogeneous dehydrogenating catalyst comprises an iridium catalyst, a rhodium catalyst, or a ruthenium catalyst.

40. The method of claim 38, wherein the homogeneous dehydrogenating catalyst comprises an iridium catalyst.

41. The method of claim 38, wherein the homogeneous dehydrogenating catalyst has the formula:wherein M is Ir, Rh, Ru, or Os; L1and L2are independently –O-, -S-, -NR6-, or substituted or unsubstituted alkylene; each R3and R4is independently substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is independently halogen, -CX53, -CHX52, -CH2X5, -OCX53, -OCH2X5, -OCHX52, -CN, -SOn5R5D, -SOv5NR5AR5B, ^NR5CNR5AR5B, ^ONR5AR5B, -NR5CC(O)NR5AR5B, -N(O)m5, -NR5AR5B, -C(O)R5C, -C(O)OR5C, -OC(O)R5C, -OC(O)OR5C, -C(O)NR5AR5B, -OC(O)NR5AR5B, -OR5D, -SR5D, -NR5ASO2R5D, -NR5AC(O)R5C, -NR5AC(O)OR5C, -NR5AOR5C, -P(O)2(OR5A), -OP(O)2(OR5A), -OP(R5A)(R5B), -BR5AR5B, -SiR5AR5BR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; each R6is independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; each R5A, R5B, R5C, and R5Dis independently hydrogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; or R5Aand R5Bsubstituents bonded to the same nitrogen atom are joined to form a substituted or unsubstituted heterocycloalkyl or substituted or unsubstituted heteroaryl; each X5is independently –Cl, -Br, -I, or –F; n5 is 0, 1, 2, 3, or 4; each m5 and v5 is independently 1 or 2; and z5 is 0, 1, 2, or 3.

42. The method of claim 38, wherein the homogeneous dehydrogenating catalyst is.

43. The method of claim 7, wherein a percentage of from 1% to 3% of monomer units in the dehydrogenated polymer are unsaturated.

44. The method of claim 7, wherein a percentage of from 1.7% to 2.1% of monomer units in the dehydrogenated polymer are unsaturated.

45. The method of claim 7, wherein a percentage of from 1.9% to 2.1% of monomer units in the dehydrogenated polymer are unsaturated.

46. The method of claim 7, wherein the dehydrogenated polymer comprises at least one –C(R1)=C(R2)- monomer unit, wherein R1is independently hydrogen, halogen, -CX13, -CHX12, -CH2X1, -OCX13, -OCH2X1, -OCHX12, -CN, -SOn1R1D, -SOv1NR1AR1B, ^NR1CNR1AR1B, ^ONR1AR1B, -NR1CC(O)NR1AR1B, -N(O)m1, -NR1AR1B, -C(O)R1C, -C(O)OR1C, -OC(O)R1C, -OC(O)OR1C, -C(O)NR1AR1B, -OC(O)NR1AR1B, -OR1D, -SR1D, -NR1ASO2R1D, -NR1AC(O)R1C, -NR1AC(O)OR1C, -NR1AOR1C, -P(O)2(OR1A), -OP(O)2(OR1A), -BR1AR1B, -SiR1AR1BR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; R2is independently hydrogen, halogen, -CX23, -CHX22, -CH2X2, -OCX23, -OCH2X2, -OCHX22, -CN, -SOn2R2D, -SOv2NR2AR2B, ^NR2CNR2AR2B, ^ONR2AR2B, -NR2CC(O)NR2AR2B, -N(O)m2, -NR2AR2B, -C(O)R2C, -C(O)OR2C, -OC(O)R2C, -OC(O)OR2C, -C(O)NR2AR2B, -OC(O)NR2AR2B, -OR2D, -SR2D, -NR2ASO2R2D, -NR2AC(O)R2C, -NR2AC(O)OR2C, -NR2AOR2C, -P(O)2(OR2A), -OP(O)2(OR2A), -BR2AR2B, -SiR2AR2BR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;each R1A, R1B, R1C, R1D, R2A, R2B, R2C, and R2Dis independently hydrogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; or R1Aand R1Bsubstituents bonded to the same nitrogen atom are joined to form a substituted or unsubstituted heterocycloalkyl or substituted or unsubstituted heteroaryl; or R2Aand R2Bsubstituents bonded to the same nitrogen atom are joined to form a substituted or unsubstituted heterocycloalkyl or substituted or unsubstituted heteroaryl; each X1and X2is independently –Cl, -Br, -I, or –F; each n1 and n2 is independently 0, 1, 2, 3, or 4; and each m1, m2, v1, and v2 is independently 1 or 2.

47. The method of claim 46, wherein R1and R2are independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH2F, -OCH2I, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, or substituted or unsubstituted C1-C20alkyl.

48. The method of claim 46, wherein R1and R2are independently hydrogen or substituted or unsubstituted C1-C1000 alkyl.

49. The method of claim 46, wherein R1and R2are hydrogen.

50. The method of claim 1, conducted under continuous flow conditions.

51. A substituted or unsubstituted dehydrogenated polyethylene, wherein a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units are unsaturated.

52. The dehydrogenated polyethylene of claim 51, having a number average molecular weight of from 1,000 Da to 500,000 Da.

53. A substituted or unsubstituted dehydrogenated polyethylene, having a number average molecular weight of 2,200 Da or greater.

54. The dehydrogenated polyethylene of claim 53, having a number average molecular weight of from 2,200 Da to 500,000 Da.

55. The dehydrogenated polyethylene of claim 53, having a number average molecular weight of from 2,200 Da to 6,500 Da or a number average molecular weight greater than 6,700 Da.

56. The dehydrogenated polyethylene of claim 53, wherein a percentage of from 0.01% to 11% of monomer units are unsaturated.

57. The dehydrogenated polyethylene of claim 53, wherein a percentage of from 0.01% to 10% of monomer units are unsaturated.

58. The dehydrogenated polyethylene of claim 53, wherein a percentage of 8% or less of monomer units are unsaturated.

59. The dehydrogenated polyethylene of claim 53, wherein a percentage of from 1.5% to 3% of monomer units are unsaturated.

60. The dehydrogenated polyethylene of claim 53, wherein a percentage of 1.9% of monomer units are unsaturated.

61. The dehydrogenated polyethylene of claim 51, wherein the distribution of unsaturated monomer units is irregular.

62. The dehydrogenated polyethylene of claim 51, comprising at least one –C(R1)=C(R2)- monomer unit, wherein R1is independently hydrogen, halogen, -CX13, -CHX12, -CH2X1, -OCX13, -OCH2X1, -OCHX12, -CN, -SOn1R1D, -SOv1NR1AR1B, ^NR1CNR1AR1B, ^ONR1AR1B, -NR1CC(O)NR1AR1B, -N(O)m1, -NR1AR1B, -C(O)R1C, -C(O)OR1C, -OC(O)R1C, -OC(O)OR1C, -C(O)NR1AR1B, -OC(O)NR1AR1B, -OR1D, -SR1D, -NR1ASO2R1D, -NR1AC(O)R1C,-NR1AC(O)OR1C, -NR1AOR1C, -P(O)2(OR1A), -OP(O)2(OR1A), -BR1AR1B, -SiR1AR1BR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; R2is independently hydrogen, halogen, -CX23, -CHX22, -CH2X2, -OCX23, -OCH2X2, -OCHX22, -CN, -SOn2R2D, -SOv2NR2AR2B, ^NR2CNR2AR2B, ^ONR2AR2B, -NR2CC(O)NR2AR2B, -N(O)m2, -NR2AR2B, -C(O)R2C, -C(O)OR2C, -OC(O)R2C, -OC(O)OR2C, -C(O)NR2AR2B, -OC(O)NR2AR2B, -OR2D, -SR2D, -NR2ASO2R2D, -NR2AC(O)R2C, -NR2AC(O)OR2C, -NR2AOR2C, -P(O)2(OR2A), -OP(O)2(OR2A), -BR2AR2B, -SiR2AR2BR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; each R1A, R1B, R1C, R1D, R2A, R2B, R2C, and R2Dis independently hydrogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; or R1Aand R1Bsubstituents bonded to the same nitrogen atom are joined to form a substituted or unsubstituted heterocycloalkyl or substituted or unsubstituted heteroaryl; or R2Aand R2Bsubstituents bonded to the same nitrogen atom are joined to form a substituted or unsubstituted heterocycloalkyl or substituted or unsubstituted heteroaryl; each X1and X2is independently –Cl, -Br, -I, or –F; each n1 and n2 is independently 0, 1, 2, 3, or 4; and each m1, m2, v1, and v2 is independently 1 or 2.

63. The dehydrogenated polyethylene of claim 62, wherein R1and R2are independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ^NHNH2, ^ONH2, ^NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH,-NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH2F, -OCH2I, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, or substituted or unsubstituted C1-C10 alkyl.

64. The dehydrogenated polyethylene of claim 62, wherein R1and R2are independently hydrogen or substituted or unsubstituted C1-C1000 alkyl.

65. The dehydrogenated polyethylene of claim 62, wherein R1and R2are hydrogen.

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