Selective hydrodehalogenation using transition metal ligand complexes

Abstract

The present disclosure describes selective hydrodehalogenation reactions involving compositions comprising transition metal ligand complexes under various conditions. Also described are product compositions, and in some cases novel compounds, resulting from such reactions.

Description

SELECTIVE HYDRODEHALOGENATION USING TRANSITION METAL LIGAND COMPLEXESFIELD

[0001] The present disclosure describes selective hydrodehalogenation reactions involving compositions comprising transition metal ligand complexes under various conditions. Also described are product compositions, and in some cases novel compounds, resulting from such reactions.BACKGROUND

[0002] Hydrodehalogenation processes, such as Hydrodefluorination (HDF), are known generally and disclosed in the published literature. HDF has been demonstrated using metal-catalyzed systems employing silanes, alanes, or hydrogen as the terminal reductants. These approaches all share a common characteristic in their mechanisms with the initial attack of a nucleophilic metal hydride on an electrophilic olefin.

[0003] Whether catalyzed or uncatalyzed, conditions vary quite a bit, as can be seen from the variety of publications enumerated below.

[0004] In Green Chem., 2022, 24, 2777-2782, the article discusses a transition-metal-free hydrodefluorination of trifluoromethyl alkenes for producing gem-difluoroalkenes. The reaction appears to be non-catalytic, requiring cesium carbonate (CS2CO3) as a base. Also discussed is the specificity of diphenylphosphine oxide, of which excess seems to be needed. The substrate scope seems focused on (limited to) alpha-beta unsaturated ketones containing a beta-trifluoromethyl substituent.

[0005] In Cheng et al., Nat. Commnn., 2021, 12, 2835, the article reported a 2° diazaphosphol ene capable of catalyzing hydrodefluorination of trifluoromethylstyrene derivatives in conjunction with PhSiHs as the terminal reductant. Depending on the number of equivalents of silane added, the reaction could allegedly be tuned to favor the difluoro- or monofluoro- olefin product.

[0006] In J. Am. Chem. Soc., 2014, 136, 4634-4639, and in New J. Chem., 2019, 43, 6897-6908, PEt3was disclosed to hydrodefluorinate fluoroarenes in the absence of metal, water, silane, or any other reductant. The authors proposed that the phosphine can act as a single-component reductant by forming the expected P-fluorophosphorane, which allegedly undergoes a hydride elimination from one of the ethyl groups to give a hydrofluorophosphorane, the P-H bond of which allegedlyundergoes substitution at the arene. The resulting Meisenheimer complex is then disclosed to eliminate the EtiPF.

[0007] Reaction of fluoroolefin with alkyl phosphines to form vinyl-fluorophosphoranes is disclosed generally in J. Am. Chem. Soc., 1979, 101, 3689-3690, and in J. Fluor. Chem., 1980, 15, 543-546. In these articles, hydrolysis of P-fluorophosphoranes with elimination of HF and phosphine oxide are disclosed to result in hydrodefluorination. However, there appears to be no disclosure of progressing the reaction all the way to the hydrodefluorinated product.

[0008] In J. Fluor. Chem., 2019, 226, 109342, Zhang el al. disclose hydrofluorocycloolefin synthesis through dehydrofluorination of hydrofluorocycloalkanes in N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMAc). The suggested key involved special acid-base properties of the amide solvents. Furthermore, the article concluded that a -CHF- bond was required for efficient dehydrofluorination, suggesting that perfluorinated cycloalkanes were inappropriate reactants in these systems.

[0009] U.S. Patent No. 10,774,021 discloses processes for preparation of hydrofluoroalkenes by selective catalytic consecutive hydrodefluorination. Such processes were disclosed to include a hydride source and a catalyst of formula LxMHz, where M is a Group 11 metal (Cu is exemplified), x and z are each integers from 1 to 4, with x+z adding to 4 or less, and L is any of a variety of ligands. Triarylphosphine catalysts are exemplified, as mono-hydrided, specifically Stryker’s reagent / Osbome complex (hexameric triphenylphospine copper hydride).

[0010] There remains a need to improve the efficacy and selectivity of hydrodehalogenation reactions. There is also a need to improve the hydrodehalogenation catalyst / ligand / complex + additive (base) combination, possibly in combination with medium(media) / solvent(s). The present disclosure identifies not only catalyst-ligand-additive systems and reaction conditions but also the unexpected yields, performance characteristics, and selectivities to specific products / product slates that can be attained through such reactions / in such systems.SUMMARY

[0011] Partially fluorinated species are not inherently easy to synthesize. The cost of fluorinated materials is coupled to their ease of synthesis and one hypothesis of hydrodefluorination is that, if it is difficult to selectively install fluorine atoms, it may be less difficult to selectively remove them.

[0012] Hydrodehalogenation (HDH) of a molecule results in the replacement of a halogen with a hydrogen. In the case of the halogen fluorine, hydrodefluorination (HDF) of a molecule results in the replacement of a fluorine with hydrogen. While this may be regarded by some as a “valueremoving” step, there are several examples of a perfluorinated species being significantly cheaper than the partially-fluorinated counterpart. One example is hexafluoropropylene (HFP) relative to the (more expensive) mono-hydrodefluorinated relative - 1, 2, 3,3,3-pentafluoropropylene (1225ye) or chlorotrifluoroethylene (CTFE) relative to l-chloro-1,2-difluoroethylene (1122a).

[0013] The present disclosure describes, among other things, processes by which nucleophilic hydrodehalogenation can be used as a route to synthesize hydrohaloolefins (e.g., HFOs, HFCOs, and the like) of commercial value, such as starting from perhalogenated (or heavily halogenated) olefin feedstocks. This nucleophilic hydrodehalogenation employs transition metal carboxylate compounds as terminal reductants, as enabled (stabilized) by heteroatom-containing (e.g., phosphorus- and / or nitrogen- containing; in particular, at least phosphorus-containing) ligand additives. If desired, the transition metal carboxylate and / or ligand additive can be regenerated by incorporation of a very strong base, e.g., a hydride source such as a silane, as a terminal reductant, such as to achieve relatively high yields of enantiomerically selective products.

[0014] Reinforcing the surprising and unexpected aspects of chemistry at times, divergent chemoselectivity can arise in various systems depending on the carb oxy late(s) and / or ligand additive(s) used. Further, even heteroatom-containing haloolefins can be hydrodehalogenated using such reaction systems, while retaining their heteroatoms within their structure - for example, perfluoro(methyl vinyl ether) (PMVE) can be converted to an E- / Z- mixture of the vinyl ether congener of 1225ye (trifluorom ethyl difluorovinyl ether; E1225ye), a compound believed to be scarcely seen, if ever, in preparative methods.

[0015] Furthermore, this chemical approach can be used to synthesize unique less halogenated (though still halogenated) products.DETAILED DESCRIPTION

[0016] As used herein, a range of values referencing real numbers [A] and [B], expressed as “between [A] and [B]”, should be understood as including [A] and [B] unless otherwise specified for either / both of [A] and [B], the same as if the range were expressed as “from [A] to [B]” or “at least [A]” or “up to [B]”.

[0017] As used herein, the terms “trihydrocarbyl”, “trialkyl”, “triaryl”, and the like, such as in reference to compounds such as phosphines herein, should be understood to encompass not only compounds (phosphines) with simply three hydrocarbyl (or alkyl or aryl or the like) moieties but more broadly to tri -substituted moieties that may be more than monofunctional. For example, with respect to phosphine compounds herein, there may be more than one phosphorus atom in a molecule connected to each other with shared hydrocarbyl (or alkyl or aryl) moieties but each being nevertheless characterizable as being “trihydrocarbyl” (or “trialkyl” or “triaryl”) individually - as non-limiting examples, please note l,2-bis(dicyclohexylphosphino)ethane, 1,2-bis(diisobutylphosphino)ethane, and l,2-bis(diphenylphosphino)ethane (Diphos) as difunctional phosphines each characterizable as “trihydrocarbyl” herein, and please also note 1,1,1-tris(diphenylphosphinomethyl)ethane (Tripod) and bis[2- (diphenylphosphino)ethyl]phenylphosphine (TriPhos) as trifunctional phosphines each characterizable as “trihydrocarbyl” herein. Indeed, despite a compound or moiety being characterized as “trihydrocarbyl” (or with similar moniker indicating a trisubstitution), it is indeed possible for two (or three) seemingly independent bonding points to a central atom (such as a phosphorus atom) be linked together to form a cyclic (or, in the case of heteroatoms, a heterocyclic) moiety / compound - a non-limiting example can include, but is not limited to, 9-isobutyl-9-phosphabicyclo[3.3.1]nonane, a phosphine with three separate carbon -phosphorus single bonds, two of which are connected to each other through a bicyclic ring, which should still be understood by the ordinary skilled artisan to be broadly characterized herein as a trihydrocarbyl / trialkyl phosphine / ligand additive.

[0018] As used herein, the term “hydrocarbyl” should be understood to refer to a moiety and / or compound containing hydrogen and carbon atoms and may therefore encompass the terms “alkyl,” “alkenyl,” “alkynyl,” “aryl” / “aromatic,” “aralkyl,” and “alkaryl,” among others. As used herein, the term “alkyl” should be understood to refer to a linear or branched, cyclic or acyclic, fully saturated hydrocarbon (with only single carbon-carbon bonds). As used herein, the term “aryl” should be understood to refer to an at least partially cyclic hydrocarbyl moiety containing in some portion (or all) of its structure conjugated carbon-carbon unsaturations (double-bonds) having aromatic character. Although “aryl” can broadly be defined herein as containing partially aromatic character, it can in some embodiments be limited to representing only hydrocarbon compounds having full and not partial aromatic character. Further, although the hydrocarbonaceouscompounds / moieties mentioned in this paragraph may permissively incorporate within their structure functional groups comprising non-metallic (and optionally but preferably also nonmetalloid) heteroatoms (e.g., oxygen, nitrogen, sulfur, halogens, etc.), such hydrocarbon moi eties can in some embodiments be limited to containing only hydrogen and carbons atoms and no other heteroatoms. Additionally or alternatively, the hydrocarbonaceous compounds / moieties mentioned in this paragraph may contain hydrogen, carbon, and optionally only oxygen, nitrogen, and / or sulfur, but no other heteroatoms. However, regarding phosphines herein, because of the nature of the phosphine moiety (as well as any other named moiety / compound implying rules governing its chemical structure), regardless of the presence or absence of heteroatoms in the full compound structure, the ordinary skilled artisan should understand that the phosphorus atom(s) therein may still (each) only be associated with (bonded to) carbon and / or hydrogen atoms.

[0019] The present disclosure describes a process for selectively hydrodehalogenating a halogen-containing reactant to form a less-halogenated unsaturated product. Although the hydrodehalogenation could encompass hydrodechlorination, hydrodeiodination, hydrodebromination, and the like, typically the hydrodehalogenation at least includes hydrodefluorination, in which case the halogen-containing reactant can advantageously contain at least one fluorine atom to be hydrodefluorinated (and optionally but preferably at least one additional halogen such as a chlorine or another fluorine atom). Further, although the halogencontaining reactant can include fully saturated carbons (only single bonds - no double or triple bonds, and no aromatic character), it is typically unsaturated and often contains a carbon-carbon double bond, to which at least one halogen (fluorine) atom to be hydrodehalogenated (hydrodefluorinated) is attached. To be clear, while the selectively hydrodehalogenating processes described herein can operate on halogen atoms not attached to an unsaturation, the halogen atoms connected to the unsaturation are typically more labile for hydrodehalogenation than halogen atoms connected to fully saturated carbon atoms. Occasionally, when multiple hydrodehalogenation events occur on the same multiply halogenated reactant, it is often the unsaturated halogen (fluorine) atoms that react first, followed by the halogen (fluorine) atoms attached to a carbon atom alpha to (one bond away from) the unsaturation. However, in some situations, even a chlorine attached to an unsaturation, for example, may not be as labile for hydrodehalogenation as a fluorine attached to a carbon alpha to an unsaturation - thehydrodehalogenation system (catalyst, ligand additive, base / silane, etc.) and / or reaction conditions / severity, among other things, may impact that selectivity.

[0020] The halogen-containing reactant can broadly contain any number of carbon atoms, it can advantageously contain from 2 to 12 carbon atoms, from 2 to 10 carbon atoms, from 2 to 8 carbon atoms, from 2 to 6 carbon atoms, from 3 to 10 carbon atoms, from 3 to 8 carbon atoms, or from 3 to 6 carbon atoms (in particular, from 2 to 8 carbon atoms, from 2 to 6 carbon atoms, from 3 to 8 carbon atoms, or from 3 to 6 carbon atoms). Non-limiting examples of halogen-containing reactants can include, but are not necessarily limited to, chlorotrifluoroethylene, tetrafluoroethylene, trifluoroethylene (1123), trichloroethylene (1120), fluorodichloroethylene, chlorodifluoroethylene (1122, 1122a), difluoroethylene (1132, 1132a), chlorofluoroethylene (1131, 1131a), hexafluoropropylene, pentafluoropropene (1225ye), tetrafluoropropene (1224yf, 1234ze), chloro-trifluoropropene (1233zd, 1233xf), trifluoropropene (1243zf), difluoropropene (1252zc), perfluoro(vinyl methyl ether), difluoro-(trifluoromethoxy)ethene, fluoro-(trifluorom ethoxy )ethene, trifluoromethoxy ethene, difluoromethoxy ethene, hexafluoro- 1,3-butadiene (2316), pentafluoro- 1,3 -butadiene, tetrafluoro- 1,3 -butadiene, trifluoro- 1,3 -butadiene, difluoro-l,3-butadiene, perfluorocyclobutene (cl316), pentafluorocyclobutene, tetrafluorocyclobutene, trifluorocyclobutene, difluorocyclobutene, heptafluorobutene (1327myz), hexafluorobutene (1336mzz), pentafluorobutene (1345cfz), tetrafluorobutene, trifluorobutene, difluorobutene, perfluorocyclopentene, heptafluorocyclopentene (cl427yz), hexafluorocyclopentene (cl436zz), pentafluorocyclopentene (cl445yfz), tetrafluorocyclopentene, trifluorocyclopentene, difluorocyclopentene, nonafluoropentene (1429mzy, 1429fz), octafluoropentene (1438mzz), heptafluoropentene (1447myfz), hexafluoropentene, pentafluoropentene, tetrafluoropentene, trifluoropentene, difluoropentene, hexafluorodihydrothiophene (e.g. , 2,2,3,4,5,5-hexafluoro-2,5-dihydrothiophene), pentafluorodihydrothiophene, tetrafluorodihydrothiophene, trifluorodihydrothiophene, difluorodihydrothiophene, perfluoro(propenyl methyl ether), trifluoromethyl tetrafluoropropenyl ether, and the like, and combinations thereof.

[0021] The selective hydrodehalogenating process can include exposing the halogen-containing unsaturated reactant to a metal carboxylate in the presence of a hydride source and also a ligand additive, for a time and at a temperature sufficient to form the less-halogenated unsaturated product.

[0022] In advantageous embodiments, the metal of the metal carboxylate can contain or be a transition metal, such as a metal from one or more of Groups 4 and 6-12 of the Periodic Table of Elements, or in some preferred embodiments from one or more of Groups 6-7, 9, and 11-12 of the Periodic Table of Elements. In particular, the catalyst can contain a transition metal selected from the group consisting of Ag, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof.

[0023] Additionally or alternatively, the carboxylate of the metal carboxylate can contain or be one or more of a naphthenate, formate, acetate, a propionate (e.g., n-propi onate), a butyrate (e.g., 4-butyrate), a pentanoate, a hexanoate, an octanoate (such as 2-ethylhexanoate), a decanoate (e.g., a caprate), a dodecanoate (e.g., a laurate), a tetradecanoate (e.g., a myristate), a hexadexanoate (e.g., a palmitate), an octadecanoate (e.g., a stearate), a tetradecenoate (e.g., a myri st oleate), a hexadecenoate (e.g., a palmitoleate), an octadecenoate (e.g., an oleate, a linoleate, a linolenate, or a combination thereof), pyrazinecarboxylate, acetylacetonate (Acac), and mixtures thereof.

[0024] Advantageously, the hydride source can contain or be a tri(Cl-C6 alkyl)silane (e.g., tri ethylsilane, triisopropylsilane, or a combination thereof), a tetra(Cl-C6 alkyl)disiloxane (e.g., 1,1,3,3-tetramethyldisiloxane), a di-(Cl-C6 alkyl) phenylsilane, a (C1-C6 alkyl)diphenylsiloxane, a poly silane (e.g., a poly(Cl-C12 alkyl)hydrosiloxane such as polymethylhydrosilane (PMHS)), lithium aluminum hydride, and mixtures thereof.

[0025] Advantageously, the ligand additive can contain, but is not necessarily limited to, a diimidopyridine, atri(C2-C18 alkyl and / or alkenyl)phosphite, an n,n’-bis(diarylphosphino)alkane, an n,n’,n”-tris(diarylphosphino)alkane, pyridine, a di(Cl-C6 alkyl)aminopyridine (e.g., 4-dimethylaminopyridine, 4-N-piperidinylpyridine, and combinations thereof), 2,2’ -bipyridine, 2,2’:6’,2”-terpyridine, 1,10-phenanthroline, 2,9-dimethyl-l,10-phenanthroline (neocuprine), bisoxazolines (e.g., (S)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole, 2,6-bis[(4S)-4,5-dihydro-4-(l-methylethyl)-2-oxazolyl]pyridine, or combinations thereof), a methanesulfonate, a monofluoro-methanesulfonate, a difluoro-methanesulfonate, a triflate (trifluoromethanesulfonate), triisopropylphosphite, tri(2-ethylhexyl)phosphite, triisodecylphosphite, tri oleylphosphite, triphenylphosphite, tritolylphosphite (e.g., tri(o-tolyl)phosphite, tri(p-tolyl)phosphite, or a mixture thereof), tris(nonylphenyl)phosphite, 1,2-bis(dicyclohexylphosphino)ethane, l,2-bis(dicyclopentylphosphino)ethane, 1,2-bis(diisobutylphosphino)ethane, l,2-bis(diphenylphosphino)ethane (Diphos), 1,1’-bis(diphenylphosphino)ferrocene, bis(2-dicyclohexylphosphinophenyl)ether (DCEphos) 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos), P,P,P',P'-tetramethyl P,P'-(9,9-dimethyl-9H-xanthene-4,5-diyl)bis[phosphonite] (Xant(P(OMe)2)2), 1,1,1-tris(diphenylphosphinomethyl)ethane (Tripod), bis[2-(diphenylphosphino)ethyl]phenylphosphine (TriPhos), N,N'-bis(2,6-diisopropylphenyl)ethane-l,2-diimine (DippDAD), and mixtures thereof.

[0026] Optionally but typically, the selective hydrodehalogenation can be performed in the presence of a solvent. Non-limiting examples of solvents can include, but are not limited to, benzene, toluene, a xylene (e.g., m-, p-, o-, or a mixture thereof), mesitylene, chlorobenzene, di chlorobenzene e.g., o-DCB), pyridine, dimethyl benzamide, dimethylaniline, anisole, methylcarbazole, methylindole, benzofuran, di phenyl ether, dibenzyl ether, diglyme, O,O’-dimethyl-ethylene glycol, dimethyl acetamide (DMAc), dimethyl formamide (DMF), dimethylsulfoxide (DMSO), sulfolane, cyclopentyl methyl ether (CPME), methyl t-butyl ether (MTBE), diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, formaldehyde, acetaldehyde, acetonitrile, petroleum distillate, petroleum spirits, kerosene, hexane, heptane, octane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, and mixtures thereof. In some embodiments, when used, the solvent(s) may comprise substantially no nitrogen atoms (e.g., thereby effectively excluding solvents such as pyridine, dimethyl benzamide, dimethylaniline, anisole, methylcarbazole, methylindole, dimethyl acetamide (DMAc), dimethyl formamide (DMF), and acetonitrile, for example).

[0027] In some embodiments, the selective hydrodehalogenation can be performed in the substantial absence of trihydrocarbyl phosphines, such as triarylphosphines (e.g., Stryker’s reagent).

[0028] In various embodiments, the selective hydrodehalogenation can be performed at a temperature from 0°C to 150°C, for example from 15°C to 120°C, from 30°C to 110°C, or from 40°C to 100°C. The reaction time can be chosen (or extended or shortened) to allow sufficient selective hydrodehalogenation reaction at a particular reaction temperature and / or within a particular temperature range.

[0029] The less halogenated product (typically unsaturated) can broadly contain any number of carbon atoms, and can typically contain the same number of carbon atoms as the halogencontaining reactant (i.e., the hydrodehalogenation process typically does not include removal of a carbon atom, and any process that can add or subtract carbon atoms is usually done separately from, whether preceding or following, the hydrodehalogenation process of this disclosure). Assuch, it can advantageously contain from 2 to 12 carbon atoms, from 2 to 10 carbon atoms, from 2 to 8 carbon atoms, from 2 to 6 carbon atoms, from 3 to 10 carbon atoms, from 3 to 8 carbon atoms, or from 3 to 6 carbon atoms (in particular, from 2 to 8 carbon atoms, from 2 to 6 carbon atoms, from 3 to 8 carbon atoms, or from 3 to 6 carbon atoms). Furthermore, as the name indicates, a less halogenated product contains at least one (and sometimes more than one) less halogen atom than its corresponding halogen-containing reactant. Due to the nature of the selective hydrodehalogenation reaction, the less halogenated (thus non-perhalogenated) product is typically unsaturated. The product also typically contains at least one fluorine atom. Although some products are hydrocarbyl, the less halogenated product can optionally contain an oxygen atom as an ether, a sulfur atom as a thioether, and / or a nitrogen atom as an amine or imine (in particular, when present, an oxygen atom as an ether or a sulfur atom as a thioether).

[0030] Non-limiting examples of less halogenated products can include, but are not necessarily limited to, trifluoroethylene (1123), trichloroethylene (1120), fluorodichloroethylene, chlorodifluoroethylene (1122, 1122a), difluoroethylene (1132, 1132a), chlorofluoroethylene (1131, 1131a), vinyl chloride (1140), pentafluoropropene (1225ye), tetrafluoropropene (1224yf, 1234ze), chloro-trifluoropropene (1233zd, 1233xf), trifluoropropene (1243zf), difluoropropene (1252zc), vinyl fluoride (1141), difluoro-(trifluoromethoxy)ethene, fluoro-(trifluoromethoxy)ethene, trifluoromethoxy ethene, difluoromethoxyethene, fluoromethoxy ethene, pentafluoro-l,3-butadiene, tetrafluoro-l,3-butadiene, trifluoro-l,3-butadiene, difluoro-1,3-butadiene, pentafluorocyclobutene, tetrafluorocyclobutene, trifluorocyclobutene, difluorocyclobutene, fluorocyclobutene, heptafluorobutene (1327myz), hexafluorobutene (1336mzz), pentafluorobutene (1345cfz), tetrafluorobutene, trifluorobutene, difluorobutene, fluorobutene, heptafluorocyclopentene (c!427yz), hexafluorocyclopentene (c!436zz), pentafluorocyclopentene (cl445yfz), tetrafluorocyclopentene, trifluorocyclopentene, difluorocyclopentene, fluorocyclopentene, nonafluoropentene (1429mzy, 1429fz), octafluoropentene (1438mzz), heptafluoropentene (1447myfz), hexafluoropentene, pentafluoropentene, tetrafluoropentene, trifluoropentene, difluoropentene, hexafluorodihydrothiophene (e.g, 2,2,3,4,5,5-hexafluoro-2,5-dihydrothiophene), pentafluorodihydrothiophene, tetrafluorodihydrothiophene, trifluorodihydrothiophene, difluorodihydrothiophene, trifluoromethyl tetrafluoropropenyl ether, and the like, and combinations thereof.

[0031] In advantageous embodiments, the less-halogenated product (typically unsaturated) can have a selectivity through the hydrodehalogenation process of at least 50%, at least 60%, at least 70%, at least 80%, at least 85%, or at least 90% (and up to and including 100%), based on a molar ratio of one or a group of desired products, relative to all reaction products (not including any unreacted reactant nor any catalyst, whether consumed or not, nor any ligand additive nor any hydride source, whether reacted or not, nor any solvent, if utilized). If the selectivity is not appropriately high and / or if one of the lesser products is seen as a particularly troublesome or undesirable, or for any other reason, the selective hydrodehalogenation process can further include a step of isolating and / or purifying one or more selective isomeric species, relative to all other products (and / or reactants). Optionally, if the reactant composition is not pure enough and / or if one of the reactant impurities is particularly susceptible to (undesirable) side reactions (or for any other reason), the selective hydrodehalogenation process may additionally or alternatively include a pre-purification step on the reactant composition.

[0032] Without being bound by theory, it is believed that the ligand additive stabilizes and / or mediates an interaction between the hydride source and the transition metal carboxylate to form a reactive transition metal hydride intermediate that is complexed with / stabilized by at least one carboxylate and / or the ligand additive. Then, it is believed that the transition metal hydride intermediate adds across a double-bond in the (typically unsaturated) halogen-containing reactant, forming a transition metal complex at one carbon and a hydrogen bonded to the other carbon of the carbon-carbon (double) bond. Whether in an apparent single step or as a transient intermediate, a selective hydrodehalogenation of a halogen proximate to the carbon complexed to the transition metal to liberate a (ligand- / carboxylate- stabilized) transition metal halide thereby completes the selective hydrodehalogenation. The transition metal halide complex can react with the hydride source to remove the halide and to regenerate the active transition metal (carboxylate) and to thereby form the fluorosubstituted hydride source. Although this reaction is encapsulated here as a single hydrodehalogenation, it is possible and sometimes even likely that more than one hydrodehalogenation reaction can occur in series.

[0033] As such, the instant disclosure describes a less-halogenated (non-perhalogenated) typically unsaturated product generally made by a selective hydrodehalogenation process such as described herein. However, the instant disclosure additionally describes “raw” (as-synthesized) compositions containing said less-halogenated (non-perhalogenated) typically unsaturatedproduct, advantageously comprising at least one fluorine atom and optionally an oxygen atom as an ether, a sulfur atom as a thioether, and / or a nitrogen atom as an amine or imine (when present, in particular an oxygen atom as an ether or a sulfur atom as a thioether). Such “raw” compositions may also contain a transition metal carboxylate (whether used and regenerated in the reaction or unused) and / or a halogen- (typically fluorine-) substituted transition metal carboxylate compound, which (as mentioned above) is believed to be an intermediate or transient compound formed during the selective hydrodehalogenation reaction. Similarly, such “raw” compositions may also contain a halogen-substituted (typically a fluorine-substituted) hydride compound, which (as mentioned above) is believed to be formed upon reaction of the hydride portion of the hydride source. Nonlimiting examples of fluorine-substituted hydride compound may include, but are not limited to, a tri(Cl-C6 alkyl)fluorosilane (e.g., triethylfluorosilane, triisopropylfluorosilane, or a combination thereof), a mono-fluoro-tetra(Cl-C6 alkyl)disiloxane (e.g., 1 -fluoro- 1,1, 3,3-tetramethyldisiloxane), a difluoro-tetra(Cl-C6 alkyl)disiloxane (e.g., 1,3 -difluoro- 1, 1,3,3-tetramethyldisiloxane), a (C1-C6 alkyl)diarylfluorosilane (e.g, methyldiphenylfluorosilane), a di-(C1-C6 alkyl)arylfluorosilane (e.g., dimethylphenyl fluorosilane), a mono-, di-, or poly- fluorosubstituted polysilane (e.g., a poly(Cl-C12 alkyl)hydrosiloxane such as polymethylhydrosilane (PMHS)), a mono-, di-, tri-, or tetra-fluoro-substituted lithium aluminum hydride, and mixtures thereof. Such “raw compositions may also contain the ligand additive, whether alone / unreacted / regenerated, as complexed / reacted with a transition metal carboxylate or complex, as reacted with a hydrogen, and / or as reacted with a halogen atom. When a solvent or mixture of solvents is present in the selective hydrodehalogenation reaction, the “raw” composition may typically also contain said solvent / mixture, which can advantageously be organic (or at least one of the solvents in a mixture of solvents is organic, rendering the mixture organic as well).

[0034] In certain advantageous embodiments, the compositions and / or the “raw” compositions may contain substantially no trihydrocarbyl phosphines (e. , in particular triarylphosphines such as Stryker’s reagent). As used herein and unless otherwise defined, the phrase “substantially no” or “in substantial absence of’ with respect to a component in a composition should be understood by the ordinary skilled artisan to mean no intentionally added amount of said component in said composition and / or no measurable amount of said component in said content However, e.g., if present as an impurity in the composition, such as through trace presence in some other component and / or via in situ formation, “substantially no” or “in substantial absence of’ can still indicatepresence of in a rather small amount, e.g, an amount of 1000 ppm by weight (wppm) or less, such as 500 wppm or less, 300 wppm or less, 200 wppm or less, 100 wppm or less, 50 wppm or less, 10 wppm or less, or about 0 wppm of said component in said composition.

[0035] Without being bound by theory, it is believed that certain less halogenated products attainable through the instantly disclosed selective hydrodehalogenation processes can be novel and never made before. An example of such a composition is shown as formula (E):wherein Ri is F, Cl, CF3, CHF2, or CFH2; each R2 is independently H, F, or Cl, with at least one R2 being H; each R3 is independently H, F, or Cl, with at least one R3 being F; R4 is (CX2)mCX , with m being 0, 1, or 2, and with each X independently being H or F but with at least one X being F; and n is 0 or 1 or 2. In a preferred embodiment of formula (E), Ri is F, CF3, CHF2, or CFH2; each R2 is independently H or F, with at least one R2 being H; both R3 are F; R4 is (CX2) in CX3, with m being 0 or 1, and with each X independently being H or F but with no more than two X’s being H; and n is 0 or 1. In particular, in formula (E): Ri is CF3, both R2 are H, both R3 are F, R4 is CF3, and n is 0 or 1; or Ri is F, both R2 are H, both R3 are F, R4 is CF3, and n is 1; or Ri is H, both R2 are F, R4 is CF3, and n is 0.Additional Embodiments

[0036] Additionally or alternatively, the present disclosure can include one or more of the following embodiments.

[0037] Embodiment 1. A process for selectively hydrodehalogenating (such as hydrodefluorinating) a halogen-containing unsaturated reactant (such as having from 2 to 12 carbon atoms, from 2 to 8 carbons, from 2 to 6 carbons, or from 3 to 6 carbons) to form a less-halogenated unsaturated product comprising selectively hydrodehalogenating the halogencontaining unsaturated reactant, by exposing it to a transition metal carboxylate in the presence of a hydride source and also a ligand additive, to form the less-halogenated unsaturated product.

[0038] Embodiment 2. The process of embodiment 1, wherein the transition metal carboxylate comprises: a transition metal selected from the group consisting of metal from one or more ofGroups 4 and 6-12 of the Periodic Table of Elements, e.g., from one or more of Groups 6-7, 9, and 11-12 of the Periodic Table of Elements, or from the group consisting of Ag, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof; and a carboxylate such as selected from the group consisting of a naphthenate, formate, acetate, a propionate (e.g., n-propi onate), a butyrate (e.g., 4-butyrate), a pentanoate, a hexanoate, an octanoate (such as 2-ethylhexanoate), a decanoate (e.g., a caprate), a dodecanoate (e.g, a laurate), a tetradecanoate (e.g, a myristate), a hexadexanoate (e.g, a palmitate), an octadecanoate (e.g., a stearate), a tetradecenoate (e.g., a myristoleate), a hexadecenoate (e.g, a palmitoleate), an octadecenoate (e.g., an oleate, a linoleate, a linolenate, or a combination thereof), pyrazinecarboxylate, acetylacetonate (Acac), and mixtures thereof.

[0039] Embodiment 3. The process of embodiment 1 or embodiment 2, wherein the hydride source comprises atri(Cl-C6 alkyl)silane (e.g., triethylsilane, triisopropylsilane, or a combination thereof), a tetra(Cl-C6 alkyl)disiloxane (e.g., 1,1,3,3-tetramethyldisiloxane), a di-(Cl-C6 alkyl) phenylsilane, a (C1-C6 alkyl)diphenylsiloxane, a polysilane (e.g., a poly(Cl-C12 alkyl)hydrosiloxane such as polymethylhydrosilane (PMHS)), lithium aluminum hydride, or a mixture thereof.

[0040] Embodiment 4. The process of any of embodiments 1-3, wherein the ligand additive comprises a diimidopyridine, a tri(C2-C18 alkyl and / or alkenyl)phosphite, an n,n’-bis(diarylphosphino)alkane, an n,n’,n”-tris(diarylphosphino)alkane, pyridine, a di(Cl-C6 alkyl)aminopyridine, 2,2’-bipyridine, 2,2’:6’,2”-terpyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline (neocuprine), (S)-4-(tert-butyl)-2-(pyri din-2 -yl)-4,5-dihydrooxazole, 2,6-bis[(4S)-4,5-dihydro-4-(l-methylethyl)-2-oxazolyl]pyridine, a methanesulfonate, a monofluoromethanesulfonate, a difluoro-methanesulfonate, a triflate (trifluoromethanesulfonate), triisopropylphosphite, tri(2-ethylhexyl)phosphite, triisodecylphosphite, tri oleylphosphite, triphenylphosphite, tritolylphosphite (e.g., tri(o-tolyl)phosphite, tri(p-tolyl)phosphite, or a mixture thereof), tris(nonylphenyl)phosphite, l,2-bis(dicyclohexylphosphino)ethane, 1,2-bis(dicyclopentylphosphino)ethane, l,2-bis(diisobutylphosphino)ethane, 1,2-bis(diphenylphosphino)ethane (Diphos), l,l’-bis(diphenylphosphino)ferrocene, bis(2-dicyclohexylphosphinophenyl)ether (DCEphos) 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos), P,P,P',P'-tetramethyl P,P'-(9,9-dimethyl-9H-xanthene-4,5-diyl)bis[phosphonite] (Xant(P(OMe)2)2), l,l,l-tris(diphenylphosphinomethyl)ethane (Tripod),bis[2-(diphenylphosphino)ethyl]phenylphosphine (TriPhos), N,N'-bis(2,6-diisopropylphenyl)ethane-l,2-diimine (DippDAD), or a mixture thereof.

[0041] Embodiment 5. The process of any of embodiments 1-4, wherein the selective hydrodehalogenation (hydrodefluorination) is performed in the presence of a solvent comprising benzene, toluene, a xylene (e.g., m-, p-, o-, or a mixture thereof), mesitylene, chlorobenzene, di chlorobenzene (e.g, o-DCB), pyridine, dimethyl benzamide, dimethylaniline, anisole, methylcarbazole, methylindole, benzofuran, diphenylether, dibenzyl ether, diglyme, dimethyl acetamide (DMAc), dimethyl formamide (DMF), cyclopentyl methyl ether (CPME), methyl t-butyl ether (MTBE), tetrahydrofuran (THF), formaldehyde, acetaldehyde, acetonitrile, petroleum distillate, petroleum spirits, kerosene, hexane, heptane, octane, cyclohexane, cycloheptane, cyclooctane, norbomane, adamantane, or a mixture thereof.

[0042] Embodiment 6. The process of any of embodiments 1-5, wherein the selective hydrodehalogenation is performed in the substantial absence of trihydrocarbyl phosphines, such as triarylphosphines.

[0043] Embodiment 7. The process of any of embodiments 1-6, wherein the selective hydrodehalogenation is performed at a temperature from 0°C to 150°C, for example from 15°C to 120°C, from 30°C to 110°C, or from 40°C to 100°C.

[0044] Embodiment 8. The process of any of embodiments 1-7, wherein the less-halogenated unsaturated product has a selectivity of at least 50%, at least 60%, at least 70%, at least 80%, at least 85%, or at least 90%.

[0045] Embodiment 9. The process of any of embodiments 1-8, further comprising a step of isolating and / or purifying one or more selective isomeric species, relative to all other products.

[0046] Embodiment 10. A composition comprising: a non-perhalogenated unsaturated product made by reaction of a transition metal carboxylate and a halogen-containing reactant, the non-perhalogenated unsaturated product comprising at least one fluorine atom and optionally an oxygen or sulfur atom as an ether or thioether, respectively; a transition metal carboxylate and / or a fluorine-substituted transition metal carboxylate compound; a fluorine-substituted hydride compound; a ligand additive; and optionally an organic solvent.

[0047] Embodiment 11. The composition of embodiment 10, wherein the non-perhalogenated unsaturated product contains from 2 to 8 carbons (or from 2 to 6 carbons or from 3 to 6 carbons) and can be selected from the group consisting of trifluoroethylene (1123), trichloroethylene(1120), fluorodi chloroethylene, chlorodifluoroethylene (1122, 1122a), difluoroethylene (1132, 1132a), chlorofluoroethylene (1131, 1131a), pentafluoropropene (1225ye), tetrafluoropropene (1224yf, 1234ze), chloro-trifluoropropene (1233zd, 1233xf), trifluoropropene (1243zf), difluoropropene (1252zc), vinyl fluoride (1141), difluoro-(trifluoromethoxy)ethene, fluoro-(trifluoromethoxy)ethene, trifluoromethoxyethene, difluoromethoxyethene, fluoromethoxyethene, pentafluoro-l,3-butadiene, tetrafluoro-l,3-butadiene, tri fluoro- 1,3 -butadiene, difluoro-1,3-butadiene, pentafluorocyclobutene, tetrafluorocyclobutene, trifluorocyclobutene, difluorocyclobutene, fluorocyclobutene, heptafluorobutene (1327myz), hexafluorobutene (1336mzz), pentafluorobutene (1345cfz), tetrafluorobutene, trifluorobutene, difluorobutene, fluorobutene, heptafluorocyclopentene (cl427yz), hexafluorocyclopentene (cl436zz), pentafluorocyclopentene (cl445yfz), tetrafluorocyclopentene, trifluorocyclopentene, difluorocyclopentene, fluorocyclopentene, nonafluoropentene (1429mzy, 1429fz), octafluoropentene (1438mzz), heptafluoropentene (1447myfz), hexafluoropentene, pentafluoropentene, tetrafluoropentene, trifluoropentene, difluoropentene, hexafluorodihydrothiophene2,2,3,4,5,5-hexafluoro-2,5-dihydrothiophene), pentafluorodihydrothiophene, tetrafluorodihydrothiophene, trifluorodihydrothiophene, difluorodihydrothiophene, trifluoromethyl tetrafluoropropenyl ether, and mixtures thereof.

[0048] Embodiment 12. The composition of embodiment 10 or embodiment 11, wherein the transition metal carboxylate comprises: a transition metal selected from the group consisting of one or more of Groups 4 and 6-12 of the Periodic Table of Elements, e.g, from one or more of Groups 6-7, 9, and 11-12 of the Periodic Table of Elements, or from the group consisting of Ag, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof; and a carboxylate such as selected from the group consisting of a naphthenate, formate, acetate, a propionate (e.g., n-propionate), a butyrate (e.g., 4-butyrate), a pentanoate, a hexanoate, an octanoate (such as 2-ethylhexanoate), a decanoate (e.g, a caprate), a dodecanoate (e.g, a laurate), a tetradecanoate (e.g, a myristate), a hexadexanoate (e.g, a palmitate), an octadecanoate (e.g., a stearate), a tetradecenoate (e.g., a myristoleate), a hexadecenoate (e.g., a palmitoleate), an octadecenoate (e.g., an oleate, a linoleate, a linolenate, or a combination thereof), pyrazinecarboxylate, acetylacetonate (Acac), and mixtures thereof.

[0049] Embodiment 13. The composition of any of embodiments 10-12, wherein the fluorinesubstituted transition metal carboxylate comprises a transition metal carboxylate in which one of the carboxylate moi eties is substituted by a fluorine atom.

[0050] Embodiment 14. The composition of any of embodiments 10-13, wherein the fluorinesubstituted hydride compound comprises a tri(Cl-C6 alkyl)fluorosilane (e.g., tri ethylfluorosilane, triisopropylfluorosilane, or a combination thereof), a mono-fluoro-tetra(Cl-C6 alkyl)disiloxane (e.g., l-fluoro-l,l,3,3-tetramethyldisiloxane), a difluoro-tetra(Cl-C6 alkyl)disiloxane (e.g., 1,3-difluoro-l,l,3,3-tetramethyldisiloxane), a (C1-C6 alkyl)diarylfluorosilane (e-g-, methyldiphenylfluorosilane), a di-(Cl-C6 alkyl)arylfluorosilane (e.g., dimethylphenyl fluorosilane), a mono-, di-, or poly- fluoro-substituted poly silane (e.g., a poly(Cl-C12 alkyl)hydrosiloxane such as polymethylhydrosilane (PMHS)), a mono-, di-, tri-, or tetra-fluoro-substituted lithium aluminum hydride, or a mixture thereof.

[0051] Embodiment 15. The composition of any of embodiments 10-15, wherein the ligand additive comprises a diimidopyridine, a tri(C2-C18 alkyl and / or alkenyl)phosphite, an n,n’-bis(diarylphosphino)alkane, an n,n’,n”-tris(diarylphosphino)alkane, pyridine, a di(Cl-C6 alkyl)aminopyridine, 2,2’-bipyridine, 2,2’:6’,2”-terpyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline (neocuprine), (S)-4-(tert-butyl)-2-(pyri din-2 -yl)-4,5-dihydrooxazole, 2,6-bis[(4S)-4,5-dihydro-4-(l-methylethyl)-2-oxazolyl]pyridine, a methanesulfonate, a monofluoromethanesulfonate, a difluoro-methanesulfonate, a triflate (trifluoromethanesulfonate), triisopropylphosphite, tri(2-ethylhexyl)phosphite, triisodecylphosphite, tri oleylphosphite, triphenylphosphite, tritolylphosphite (e.g., tri(o-tolyl)phosphite, tri(p-tolyl)phosphite, or a mixture thereof), tris(nonylphenyl)phosphite, l,2-bis(dicyclohexylphosphino)ethane, 1,2-bis(dicyclopentylphosphino)ethane, l,2-bis(diisobutylphosphino)ethane, 1,2-bis(diphenylphosphino)ethane (Diphos), l,l’-bis(diphenylphosphino)ferrocene, bis(2-dicyclohexylphosphinophenyl)ether (DCEphos) 4,5-bis(diphenylphosphino)-9,9-di methylxanthene (Xantphos), P,P,P',P'-tetramethyl P,P'-(9,9-dimethyl-9H-xanthene-4,5-diyl)bis[phosphonite] (Xant(P(OMe)2)2), l,l,l-tris(diphenylphosphinomethyl)ethane (Tripod), bis[2-(diphenylphosphino)ethyl]phenylphosphine (TriPhos), N,N'-bis(2,6-diisopropylphenyl)ethane-l,2-diimine (DippDAD), or a mixture thereof.

[0052] Embodiment 16. The composition of any of embodiments 10-15, wherein the organic solvent is present and comprises benzene, toluene, a xylene (e.g., m-, p-, o-, or a mixture thereof), mesitylene, chlorobenzene, di chlorobenzene (e.g., o-DCB), pyridine, dimethyl benzamide, dimethylaniline, anisole, methylcarbazole, methylindole, benzofuran, di phenyl ether, dibenzyl ether, diglyme, dimethyl acetamide (DMAc), dimethyl formamide (DMF), cyclopentyl methylether (CPME), methyl t-butyl ether (MTBE), tetrahydrofuran (THF), formaldehyde, acetaldehyde, acetonitrile, petroleum distillate, petroleum spirits, kerosene, hexane, heptane, octane, cyclohexane, cycloheptane, cyclooctane, norbomane, adamantane, or a mixture thereof.

[0053] Embodiment 17. The composition of any of embodiments 10-16, wherein the composition comprises substantially no trihydrocarbyl phosphines, such as triarylphosphines.

[0054] Embodiment 18. A composition of formula (E):wherein Ri is F, Cl, CF3, CHF2, or CFH2; each R2 is independently H, F, or Cl, with at least one R2 being H; each R3 is independently H, F, or Cl, with at least one R3 being F; R4 is (CX2)mCX , with m being 0, 1, or 2, and with each X independently being H or F but with at least one X being F; and n is 0 or 1 or 2.

[0055] Embodiment 19. The composition of embodiment 18, wherein Ri is F, CF3, CHF2, or CFH2; each R2 is independently H or F, with at least one R2 being H; both R3 are F; R4 is (CX2)mCX3, with m being 0 or 1, and with each X independently being H or F but with no more than two X’s being H; and n is 0 or 1.

[0056] Embodiment 20. The composition of embodiment 19, wherein Ri is CF3; both R2 are H; both R3 are F; R4 is CF3; and n is 0 or 1.

[0057] Embodiment 21. The composition of embodiment 19, wherein Ri is F; both R2 are H; both R3 are F; R4 is CF3; and n is i.

[0058] Embodiment 22. The composition of embodiment 19, wherein Ri is H; both R2 are F; R4 is CF3; and n is 0.

[0059] Embodiment 23. The composition of embodiment 19, wherein Ri is F; one R2 is F, while the other R2 is H; R4 is CF3; and n is 0.

[0060] The following Examples are intended to support and / or exemplify, but not necessarily limit, the scope of the invention, as recited in the claims. In this disclosure, the roots of the inclusive words “comprising”, “containing”, and “including” can alternatively encompass exclusionary or semi -exclusionary terms, such as variations of “consisting of’ and / or “consistingessentially of’, respectively, the latter of which should be understood to be given the meaning provided by United States case law as of the fding and / or priority date(s) hereof, as applicable. EXAMPLESExamples 1-61, Hydrodefluorination of hexafluoropropylene (HFP; C3F6)

[0061] Example 1 was conducted on a ~0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, copper (II) 2-ethylhexanoate (Cu(EH)2; ~4.5 mg, -0.0123 mmol, -10 mol%), l,2-bis(diphenylphosphino)ethane (DPPE / diphos; -4.9 mg, -0.0123 mmol, -10 mol%), 1,1,3,3-tetramethyldisilane (TMDS) (-10 equivalents, -1.23 mmol, -165 mg), and HFP (-0.123 mmol, -3 mL) were added, with dilution by benzene (CeDe) as a solvent to -600 pL. In this Example, the concentration ratio of reactant to solvent was -0.3 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap. Reaction temperature was ~45°C, and the reaction was run for -2 hours. Reaction progress was monitored using19F NMR on a 500 MHz Bruker Avance III™ instrument at room temperature (~17-23°C), and conversions were calculated based on the relative integration of signals in19F NMR, using PI1CF3 (8 - -63.5 ppm) and / or fluorinated siloxane (8 ~ -130.7 ppm) as internal reference standard(s). In this case, conversion was calculated at -6%, with products being -3% E-1225ye, -3% Z-1225ye, -0% 1234yf, and -0% 1252zc. See the reaction scheme below.

[0062] Example 2 was identical to Example 1, except that it was run for -18 hours. In this case, conversion was calculated at -28%, with products being -9% E-1225ye, -19% Z-1225ye, -0% (trace) 1234yf, and~0% 1252zc.

[0063] Example 3 was identical to Example 1, except that copper (II) naphthenate (Cu(Nap)2) was used at the same molar concentration of -10 mol% instead of Cu(EH)2. In this case, conversion was calculated at -80%, with products being -66% E-1225ye, -14% Z-1225ye, -0% (trace) 1234yf, and -0% 1252zc.

[0064] Example 4 was identical to Example 3, except that it was run for -18 hours. In this case, conversion was calculated at -100% (essentially complete), with products being -0% (trace) E-1225ye, -0% (trace) Z-1225ye, -94% 1234yf, and -6% 1252zc.

[0065] Example 5 was identical to Example 4, except that copper (IT) stearate (Cu(St)2) was used at the same molar concentration of -10 mol% instead of Cu(Nap)2. In this case, conversion was calculated at -100% (essentially complete), with products being -0% (trace) E-1225ye, -0% (trace) Z-1225ye, -92% 1234yf, and -8% 1252zc.

[0066] Examples 6-11 were each identical to Example 4, except that different ligand additives were substituted for DPPE, each at tripled molar concentrations of -30 mol% - trimethylphosphite (P(OMe)3j Example 6), tri ethyl phosphite (P(OEt)s; Example 7), tributylphosphite (P(OBu)s; Example 8), tri(2-ethylhyxyl)phosphite (TEHP; Example 9), triisodecylphosphite (TIDP; Example 10), and tri oleylphosphite (TOP; Example 11). In all these cases, conversions were calculated at -100% (essentially complete). The products in each case were: Example 6 — 31% E-1225ye, ~32%Z-1225ye, -35% 1234yf, -1% 1252zc, and the balance 236ea; Example 7 — 2%E-1225ye, -7% Z-1225ye, -77% 1234yf, -12% 1252zc, and the balance 236ea; Example 8 — 0% (trace) E-1225ye, -6% Z-1225ye, -67% 1234yf, -22% 1252zc, and the balance 236ea and 254eb; Example 9 - -0% (trace) E-1225ye, -16% Z-1225ye, -23% 1234yf, -58% 1252zc, and the balance 236ea and 254eb; Example 10 - -0% (trace) E-1225ye, -9% Z-1225ye, -44% 1234yf, -41% 1252zc, and the balance 236ea and 254eb; and Example 11 - -0% (trace) E-1225ye, -1% Z-1225ye, -39% 1234yf, -54% 1252zc, and the balance 236ea and 254eb.

[0067] Example 12 was conducted on a -0.123 mmol scale. To a 7” Nuclear Magentic Resonance (NMR) tube in a nitrogen-fdled glovebox, Chromium(III) 2-ethylhexanoate (Cr(EH)3; -28.3 mg, -0.049 mmol, -40 mol%), N,N'-Bis(2,6-diisopropylphenyl)ethane-l,2-diimine (Dipp-DAD; -18.5 mg, -0.049 mmol, -40 mol%), 1,1,3,3-tetramethyldisilane (TMDS) (-10 equivalents, -1.23 mmol, -165 mg), and HFP (0.123 mmol, -3 m ) were added, with dilution by benzene (CeDe) as a solvent to -600 pL. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafdm around the cap. Reaction temperature was ~50°C, and the reaction was run for -18 hours. Reaction progress was monitored using19F NMR on a 500 MHz Bruker Avance III™ instrument at room temperature (~17-23°C), and conversions were calculated based on the relative integration of signals in19F NMR, using PhCFs (5 ~ -63.5 ppm) and / or fluorinated siloxane (6 « -130.7 ppm) as internal reference standard(s). In this case, conversion was calculated at -100% (essentially complete), with products being -38% E-1225ye, -27% Z-1225ye, -34% 1234yf, and -1% 1252zc.

[0068] Example 13 was identical to Example 12, except that copper (IT) 2-ethyl hexanoate (CU(EH)2) was used at the same molar concentration of ~40 mol% instead of Cr(EH)2. In this case, conversion was calculated at -71), with products being -0% E-1225ye, -0% Z-1225ye, -71% 1234yf, and -0% 1252zc.

[0069] Examples 14-17 were identical to Example 12, except that different transition metal catalysts were substituted for Cr(EH)2, each at the molar concentration of -40 mol% - cobalt (II) 2-ethylhexanoate (Co(EH)2; Example 14), molybdenum (II) 2-ethylhexanoate (Mo(EH)2; Example 15); manganese (II) naphthenate (Mn(Nap)2; Example 16), and nickel (II) 2-ethylhexanoate (Ni(EH)2; Example 17). In all cases, conversions were calculated at -0% (essentially no reaction), with essentially no observed products.

[0070] Examples 18 and 19 were identical to Example 13, except that different ligand additives were substituted for Dipp-DAD, each at the same molar concentration of -40 mol% - 2,2'-bis(diphenylphosphino)-l,l'-binaphthyl (BINAP; Example 18) and 1,1’-bis(diphenylphosphino)ferrocene (DPPF; Example 19). In each case, the conversion was calculated at -100% (essentially complete). The products in each case were: Example 18 — 0% E-1225ye, -0% Z-1225ye, -15% 1234yf, and -85% 1252zc; and Example 19 - -2% E-1225ye, -57% Z-1225ye, -31% 1234yf, and -10% 1252zc.

[0071] Example 20 was identical to Example 2, except that triphenylphosphite (TPP) was substituted for DPPE ligand additive at a tripled molar concentration of -30 mol% and at a reaction temperature of ~50°C. In this case, conversion was calculated at -85%, with products being -50% E-1225ye, -30% Z-1225ye, -5% 1234yf, and -0% 1252zc.

[0072] Example 21 was identical to Example 20, except that the catalyst concentration was halved to -5 mol% and the ligand additive concentration was halved to -15 mol%. In this case, conversion was calculated at -95%, with products being -53% E-1225ye, -31% Z-1225ye, -11% 1234yf, and -0% 1252zc.

[0073] Example 22 was identical to Example 20, except that tris(nonylphenyl)phosphite (TNPP) was substituted for ligand additive TPP at the same molar concentration of -30 mol%. In this case, conversion was calculated at -83%, with products being -32% E-1225ye, -41% Z-1225ye, -10% 1234yf, and -0% 1252zc.

[0074] Example 23 was identical to Example 22, except that the catalyst concentration was halved to -5 mol% and the ligand additive concentration was halved to -15 mol%. In this case,conversion was calculated at -28%, with products being -14% E-1225ye, -13% Z-1225ye, -1% 1234yf, and -0% 1252zc.

[0075] Example 24 was identical to Example 20, except that triisopropylphosphite (TIPP) was substituted for ligand additive TPP at the same molar concentration of -30 mol%. In this case, conversion was calculated at -100% (essentially complete), with products being -0% E-1225ye, ~17%Z-1225ye, -60% 1234yf, and -23% 1252zc.

[0076] Example 25 was identical to Example 20, except that trimethylphosphite (P(OMe)3) was substituted for ligand additive TPP at the same molar concentration of -30 mol%. In this case, conversion was calculated at -100% (essentially complete), with products being -2% E-1225ye, -3% Z-1225ye, -86% 1234yf, and -9% 1252zc.

[0077] Example 26 was identical to Example 25, except that the catalyst concentration was halved to -5 mol% and the ligand additive concentration was halved to -15 mol%. In this case, conversion was calculated at -100% (essentially complete), with products being -15% E-1225ye, -16% Z-1225ye, -67% 1234yf, and -2% 1252zc.

[0078] Example 27 was identical to Example 19, except that chromium (III) 2-ethylhexanoate (Cr(EH)3) catalyst was substituted for Cu(EH)2 at the same molar concentration of -40 mol%. In this case, conversion was calculated at -84%, with products being -56% E-1225ye, -27% Z-1225ye, -1% 1234yf, and -0% 1252zc.

[0079] Examples 28 and 29 were identical to Example 27, except that different ligand additives were substituted for DPPF, each at the same molar concentration of -40 mol% - 2,2'-bis(diphenylphosphino)-l,l'-binaphthyl (BINAP; Example 28) and bis[2-(diphenylphosphino)ethyl]phenylphosphine (TriPhos; Example 29). In these cases, conversion was calculated at -67% for Example 28 and -100% (essentially complete) for Example 29. The products in each case were: Example 28 — 45% E-1225ye, -22% Z-1225ye, -0% 1234yf, and -0% 1252zc; and Example 29 - -18% E-1225ye, -17% Z-1225ye, -62% 1234yf, and -3% 1252zc.

[0080] Examples 30-32 were identical to Example 6, except that the concentration of TDMS was reduced in each case from -10 mol% to -8 mol% (Example 30), -5 mol% (Example 31), and -2 mol% (Example 32). In each case, conversion was calculated at -100% (essentially complete). The products in each case were: Example 30 - -23% E-1225ye, -22% Z-1225ye, -54% 1234yf,and ~1% 1252zc; Example 31 - -13% E-1225ye, -15% Z-1225ye, -70% 1234yf, and -2% 1252zc; and Example 32 - -31% E-1225ye, -32% Z-1225ye, -36% 1234yf, and -1% 1252zc.

[0081] Examples 33-36 were identical to Example 31, except that the solvent was changed at the same concentration / amount from benzene to cyclopentyl methyl ether (CPME; Example 33), ortho-dichlorobenzene (o-DCB; Example 34), dimethylacetamide (DMAC; Example 35), and toluene (Example 36). In each case, conversion was calculated at -100% (essentially complete). The products in each case were: Example 33 — 45% E-1225ye, -35% Z-1225ye, -0% 1234yf, and -20% 1252zc; Example 34 - -34% E-1225ye, -29% Z-1225ye, -37% 1234yf, and -0% 1252zc; Example 35 - -9% E-1225ye, -0% Z-1225ye, -90% 1234yf, and -1% 1252zc; and Example 36 - -53% E-1225ye, -43% Z-1225ye, -0% (trace) 1234yf, and -4% 1252zc.

[0082] Examples 37-42 were identical to Example 1, except that different transition metal catalysts were substituted for Cu(EH)2, each at the same molar concentration of -10 mol% -copper (II) acetate (Cu(OAc)2; Example 37), copper (II) triflate (Cu(OTf)2; Example 38), copper (II) propionate (Cu(OPr)2; Example 39), copper (II) pyrazinecarboxylate (Cu(Opyz)2; Example 40), copper (II) cyclohexyl-4-butyrate (Cu(OCyBu)2; Example 41), and copper (II) oleate (Cu(01e)2; Example 42). In addition, reaction temperature in each of Examples 37-42 was ~90°C, the solvent was m-xylene, the TMDS concentration was reduced in each case from -10 equivalents to -1.5 equivalents, and the concentration ratio of reactant to solvent was -0.175 Molar. Example 38 exhibited -0% (essentially no) conversion. Example 40 exhibited -20% conversion, and it was noted that the copper catalyst was not fully soluble in the solvent medium. In all other cases (Examples 37, 39, and 41-42), conversion was calculated at -100% (essentially complete). The products were: Example 37 — 16% E-1225ye, -24% Z-1225ye, -60% 1234yf, and -0% 1252zc; Example 39 - -22% E-1225ye, -34% Z-1225ye, -44% 1234yf, and -0% 1252zc; Example 40 --12% E-1225ye, -8% Z-1225ye, -0% 1234yf, and -0% 1252zc; Example 41 - -17% E-1225ye, -33% Z-1225ye, -50% 1234yf, and -0% 1252zc; and Example 42 - -13% E-1225ye, -26% Z-1225ye, -61% 1234yf, and -0% 1252zc. In these Examples, there was no internal NMR standard reference.

[0083] Example 43 was identical to Example 40, except that the reaction time was extended to -21 hours. In this case, conversion was calculated at -100% (essentially complete), and products were -35% E-1225ye, -27% Z-1225ye, -38% 1234yf, and -0% 1252zc.

[0084] Examples 44-53 were identical to Example 37, except that different transition metal catalysts were substituted for Cu(0Ac)2, each at the same molar concentration of -10 mol% -copper (II) naphthenate (Cu(Nap) ; Example 44), copper (II) 2-ethylhexanoate (Cu(EH)2; Example 45), molybdenum (II) 2-ethylhexanoate (Mo(EH)2j Example 46), chromium (III) 2-ethylhexanoate (Cr(EH)s; Example 47), chromium (III) naphthenate (Cr(Nap)s; Example 48), manganese (II) naphthenate (Mn(Nap)2; Example 49), cobalt (II) 2-ethylhexanoate (Co(EH)2; Example 50), nickel (II) octanoate (Ni(Oct)2; Example 51), zinc (II) 2-ethylhexanoate (Zn(EH)2; Example 52), and calcium (II) 2-ethylhexanoate (Ca(EH)2; Example 53). In addition, reaction temperature in each of Examples 44-53 was reduced to ~80°C, the reaction time was extended to -16 hours, and the TMDS concentration was reduced in each case from ~1.5 equivalents to -1 equivalent. Examples 46, 51 and 53 each exhibited -0% (essentially no) conversion, while Examples 48-49 each exhibited <5% (only trace) conversion. Example 50 exhibited -18% conversion, and Example 47 exhibited -38% conversion. The remaining Examples (44, 45, and 52) each exhibited -100% (essentially complete) conversion. The products were: Example 44 — 0% E-1225ye, -19% Z-1225ye, -77% 1234yf, and -4% 1252zc; Example 45 - -17% E-1225ye, -34% Z-1225ye, -49% 1234yf, and -0% 1252zc; Example 47 - -24% E-1225ye, -14% Z-1225ye, -0% 1234yf, and -0% 1252zc; Example 48 - -0% (trace) E-1225ye, -0% (trace) Z-1225ye, -0% 1234yf, and -0% 1252zc; Example 49 - -0% (trace) E-1225ye, -0% (trace) Z-1225ye, -0% 1234yf, and -0% 1252zc; Example 50 - -7% E-1225ye, -77% Z-1225ye, -0% 1234yf, and -0% 1252zc; and Example 52 - -52% E-1225ye, -35% Z-1225ye, -13% 1234yf, and -0% 1252zc.

[0085] Example 54(a) was identical to Example 44, except that the catalyst chromium (III) acetate (Cr(OAc)s) was substituted for Cu(OAc)2. In addition, trimethylphosphite was substituted for the ligand additive DPPE and its molar concentration was tripled to -30 mol%. Also, the reaction time was extended to 24 hours. This resulted in -0% (essentially no) conversion. In Example 54(b), the reaction temperature was increased to ~100°C, but this still resulted in -0% (essentially no) conversion.

[0086] Examples 55(a) and 55(b) were identical to Examples 54(a) and 54(b), respectively, except that the ligand additive was changed in both cases to DPPE and molar concentrations were each reduced to -10 mol%. In both Examples (at ~80°C and ~100°C), -0% (essentially no) conversion was observed.

[0087] Examples 56(a) and 56(b) were identical to Examples 55(a) and 55(b), respectively, except that the ligand additive was changed in both cases to 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos). In both Examples (at ~80°C and ~100°C), -0% (essentially no) conversion was observed.

[0088] Example 57 was identical to Example 54(a), except that the Cr(OAc)s catalyst was substituted with silver (I) acetate (Ag(OAc)) at the same concentration of ~10 mol%, and the reaction time was reduced to -18 hours. In this case, -0% (essentially no) conversion was observed.

[0089] Examples 58-61 represent a single reaction where samples were taken at reaction times of ~1 hour (Example 58), -3 hours (Example 59), -6 hours (Example 60), and ~24 hours (Example 61). These Examples collectively encompass a reaction identical to Example 57, except that the trimethylphosphite ligand additive was replaced with l,2-bis(diphenylphosphino)ethane (DPPE) and its molar concentration was reduced to -10 mol%. In addition, the reaction temperature was decreased to ~45°C. As reaction time increased, the following conversions were calculated: -69% (Example 58), -90% (Example 59), -97% (Example 60), and -100% (essentially complete; Example 61). In these respective cases, the products were: Example 58 - -34% E-1225ye, -35% Z-1225ye, -0% 1234yf, and -0% 1252zc; Example 59 - -45% E-1225ye, -45% Z-1225ye, -0% 1234yf, and -0% 1252zc; Example 60 - -48% E-1225ye, -49% Z-1225ye, -0% 1234yf, and -0% 1252zc; and Example 61 - -50% E-1225ye, -50% Z-1225ye, -0% 1234yf, and -0% 1252zc. Examples 62-74. Hydrodefluorination of Trifluoroethylene (VF3 / 1123; C2F3H)

[0090] Example 62 was conducted on a -0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-fdled glovebox, copper (II) naphthenate (CufNap)?; -9.3 mg, -0.0123 mmol, -10 mol%), methyldiphenylphosphine (PMePhs; -7.4 mg, -0.037 mmol, -30 mol%), 1,1,3,3-tetramethyldisilane (TMDS) (-1 equivalent, -0.123 mmol, -50.3 mg), and VF3 (-0.123 mmol, -3 mL) were added, with dilution by benzene (CeDe) as a solvent to -600 pL. In this Example, the concentration ratio of reactant to solvent was -0.175 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafdm around the cap. Reaction temperature was room temperature (~17-23°C), and the reaction was run for -16 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR. In this case, conversion was calculated at -17%, with products being -10% Z-l 132 and-7% E-l 132. As noted in the reaction scheme below, substantially no 1132a (VF2) was observed in the product.

[0091] Example 63 was identical to Example 62, except that the reaction temperature was ~65°C instead of room temperature. In this case, conversion was calculated to be -34%, with products being -24% Z-l 132 and -10% E-l 132.

[0092] Examples 64-65 were identical to Examples 62-63, except that the PMePh2 ligand additive was replaced by trimethylphosphite (P(OMe)a) at the same concentration of -30 mol%. In both Examples (at room temperature and ~65°C), -0% (essentially no) conversion was observed.

[0093] Example 66 was identical to Example 62, except that the PMePh ligand additive was replaced by l,2-bis(diphenylphosphino)ethane (DPPE) at a reduced concentration of -10 mol%. In this case, conversion was calculated to be -20%, with products being -18% Z-l 132 and -2% E-l 132.

[0094] Example 67 was identical to Example 66, except that the DPPE ligand additive was replaced by 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos) at the same concentration of -10 mol%. In this case, conversion was calculated to be -100% (essentially complete), with products being -95% Z-l 132 and -5% E-l 132.

[0095] Example 68 was identical to Example 67, except that the reaction time was reduced to -1 hour. In this case, conversion was calculated to be -33% (essentially complete), with products being -31% Z-l 132 and -2% E-l 132.

[0096] Example 69 was identical to Example 66, except that the DPPE ligand additive was replaced by l,l’-bis(diphenylphosphino)ferrocene (DPPF) at the same concentration of -10 mol%. In this case, conversion was calculated to be -23%, with products being -21% Z-l 132 and -2% E-l 132.

[0097] Example 70 was identical to Example 69, except that the reaction time was reduced to -4 hours and the reaction temperature was increased to ~90°C. In this case, conversion was calculated to be -72%, with products being -63% Z-l 132 and -9% E-l 132.

[0098] Example 71 was identical to Example 68, except that the XantPhos ligand additive was replaced by P,P,P',P'-Tetramethyl-P,P'-(9,9-dimethyl-9H-xanthene-4,5-diyl)bis[phosphonite] (Xant(POMe2)2) at the same concentration of -10 mol%. In this case, conversion was calculated to be -20%, with products being -19% Z-l 132 and -1% E-l 132.

[0099] Example 72 was identical to Example 71, except that the reaction time was increased to -16 hours. In this case, conversion was calculated to be -65%, with products being -61% Z-l 132 and -4% E-l 132.

[0100] Example 73 was identical to Example 71, except that the reaction temperature was increased to ~80°C. In this case, conversion was calculated to be -45%, with products being -40% Z-l 132 and -5% E-l 132.

[0101] Example 74 was identical to Example 73, except that the reaction time was increased to -16 hours. In this case, conversion was calculated to be -75%, with products being -65% Z-l 132 and -10% E-l 132.Examples 75-87. Hydrodefluorination of Chlorotri fluoroethylene (CTFE; C2F3CI)

[0102] Examples 75-76 were each conducted on a -0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-fdled glovebox, chromium (III) 2-ethylhexanoate (Cr(EH)s; -7.0 mg, -0.0123 mmol, -10 mol%), trimethylphosphite (P(OMe)s; -9.3 mg, -0.037 mmol, -30 mol%), 1,1,3,3-tetramethyldisilane (TMDS) (-5 equivalent, -0.615 mmol, -82.5 mg), and CTFE (-0.123 mmol, -3 mL) were added, with dilution by benzene (CeDe) as a solvent to -600 pL. In this Example, the concentration ratio of reactant to solvent was -0.273 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafdm around the cap. Reaction temperature was ~70°C, and the reaction was run for -18 hours (Example 75) or -72 hours (Example 76). Reaction progress was monitored using19F NMR on a 500 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR, using PhCFs (5 « -63.5 ppm) as an internal reference standard. In these cases, conversions were calculated at -89% (Example 75) and -100% (essentially complete; Example 76), with products being: Example 75 — 45% E-l 122a and -44% Z-l 122a; and Example 76 --49% E- 1122a and -51 % Z- 1122a. See the reaction scheme below.

[0103] Examples 77-78 were identical to Examples 75-76, respectively, except that the P(OMe)a ligand additive was replaced by triethylphosphite (P(OEt)3). In these cases, conversions were calculated at -33% (Example 77) and -60% (Example 78), with products being: Example 77 --17% E-l 122a and -16% Z-l 122a; and Example 78 - -30% E-l 122a and -30% Z-l 122a.

[0104] Examples 79-80 were identical to Examples 75-76, respectively, except that the P(OMe) ligand additive was replaced by tributylphosphite (P(0Bu)3). In these cases, conversions were calculated at -32% (Example 79) and -54% (Example 80), with products being: Example 79 --16% E-l 122a and -16% Z-l 122a; and Example 80 - -27% E-l 122a and -27% Z-l 122a.

[0105] Examples 81-82 were identical to Examples 75-76, respectively, except that theP(OMe)3 ligand additive was replaced by tri(2-ethylhyxyl)phosphite (TEHP). In these cases, conversions were calculated at -48% (Example 81) and -60% (Example 82), with products being: Example 81 - -24% E-l 122a and -24% Z-l 122a; and Example 82 - -30% E-l 122a and -30% Z-l 122a.

[0106] Examples 83-84 were identical to Examples 75-76, respectively, except that the P(0Me)3 ligand additive was replaced by triisodecylphosphite (TIDP). In these cases, conversions were calculated at -33% (Example 83) and -38% (Example 84), with products being: Example 83 --17% E-l 122a and -16% Z-l 122a; and Example 84 - -19% E-l 122a and -19% Z-l 122a.

[0107] Examples 85-86 were identical to Examples 75-76, respectively, except that the P(OMe)a ligand additive was replaced by trioleylphosphite (TOP). In these cases, conversions were calculated at -77% (Example 85) and -100% (essentially complete; Example 86), with products being: Example 85 — 37% E-l 122a and -40% Z-l 122a; and Example 86 — 47% E-l 122a and -53% Z-l 122a.

[0108] Example 87 was identical to Example 75, except that no ligand was used. In this case, conversion was calculated at -12%, with products being -6% E-l 122a and -6% Z-l 122a.Examples 88-93, Hydrodefluorination of El -Difluoroethylene (VF2 / 1132a; C2F2H2)

[0109] Example 88 was conducted on a -0.123 mmol scale (~3mL gaseous). To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, copper (II) naphthenate (Cu(Nap)2; -9.3 mg, -0.025 mmol, -10 mol%), trimethylphosphite (P(OMe)3; -4.6 mg, -0.037mmol, ~30 mol%), 1,1, 3, 3 -tetramethyl di si lane (TMDS) (-1 equivalent, -0.123 mmol, -16.5 mg), and VF2 (-0.123 mmol, -3 mL) were added, with dilution by m-xylene as a solvent. In this Example, the concentration ratio of reactant to solvent was -0.175 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap. Reaction temperature was room temperature (~17-23°C), and the reaction was run for -18 hours. Reaction progress was monitored using19F NMR on a 500 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR without any internal reference standards. In this case, -0% (essentially no) conversion to vinyl fluoride (1-fluoroethylene / l 141) was observed.

[0110] Example 89 was identical to Example 88, except that the reaction time was reduced to -2 hours and the reaction temperature was increased to ~90°C. In this case, conversion was calculated to be -10% to 1141 product.

[0111] Example 90 was identical to Example 89, except that the reaction time was increased to -96 hours. In this case, conversion was calculated to be -45% to 1141 product.

[0112] Example 91 was identical to Example 88, except that the trimethylphosphite ligand additive was replaced by l,2-bis(diphenylphosphino)ethane (DPPE) and the concentration reduced to -10 mol%. Still, -0% (essentially no) conversion was observed.

[0113] Example 92 was identical to Example 91 except that the reaction time was reduced to -2 hours and the reaction temperature was increased to ~90°C. In this case, conversion was calculated to be -27% to 1141 product.

[0114] Example 93 was identical to Example 92, except that the reaction time was increased to -96 hours. In this case, conversion was calculated to be -100% (essentially complete) to 1141 product.Examples 94-98. Hydrodefluorination of Perfluorocyclobutene (PFCB / 1316c; C4F6)

[0115] Example 94 was conducted on a -0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, copper (II) naphthenate (Cu(Nap)2; -5 mg, -0.006 mmol, -5 mol%) mixed with -500 pL of benzene, trimethylphosphite (P(OMe)s; -2.5 mg, -0.0202 mmol, -16.5 mol%), 1,1, 3, 3-tetramethyl disilane (TMDS) (-0.5 equivalents, -0.0615 mmol, -8.0 mg), and PFCB (-0.123 mmol, -3.0 mL; via syringe) were added. In this Example, the concentration ratio of mmol of reactant per mL of solvent was -0.246 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around thecap. Reaction temperature was room temperature (~17-23°C), and the reaction was run for -4 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrume\nt, and conversions were calculated based on the relative integration of signals in19F NMR without any internal reference standards. In this case, conversion was calculated to be ~81 %, with products being -76% 1,3,3,4,4-pentafluorocyclobutene, -5% 3,3,4,4-tetrafluorocyclobutene, -0% 1,4,4-trifluorocyclobutene, -0% 1,2-difluorocyclobutene, and -0% 1 -fluorocyclobutene.

[0116] Example 95 was identical to Example 94, except that the TMDS concentration was increased from -0.5 equivalents to -1 equivalent. In this case, conversion was calculated to be -99% (essentially complete), with products being -1% 1,3,3,4,4-pentafluorocyclobutene, -95% 3,3,4,4-tetrafluorocyclobutene, -3% 1,4,4-trifluorocyclobutene, -0% 1,2-difluorocyclobutene, and -0% 1 -fluorocyclobutene.

[0117] Example 96 was identical to Example 94, except that the concentrations of the Cu(Nap)2 catalyst and P(OMe)3 ligand additive were doubled to -10 mol% and -33 mol%, respectively, the concentration of TDMS was tripled to -1.5 equivalents, the reaction temperature was increased to ~70°C, and the reaction time was also increased to -16 hours. In this case, conversion was calculated to be -100% (essentially complete), with products being -0% 1, 3, 3,4,4-pentafluorocyclobutene, -12% 3,3,4,4-tetrafluorocyclobutene, -88% 1,4,4-trifluorocyclobutene, -0% 1,2-difluorocyclobutene, and -0% 1 -fluorocyclobutene.

[0118] Example 97 was identical to Example 96, except that the P(OMe)s ligand additive was replaced with 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos) and the concentration decreased to -10 mol%. In addition, the reaction temperature was decreased to ~45°C, and the reaction time was increased to -24 hours. In this case, conversion was calculated to be -100% (essentially complete), with products being -0% 1,3,3,4,4-pentafluorocyclobutene, -8% 3,3,4,4-tetrafluorocyclobutene, -17% 1,4,4-trifluorocyclobutene, -62% 1,2-difluorocyclobutene, and -13% 1-fluorocyclobutene.

[0119] Comparative Example 98 was identical to Example 96, except that the Cu(Nap)2 catalyst was replaced by Stryker’s catalyst (CuHPPln as formula, but represented *6 as bipyramidal copper complex) at the same concentration of -10 mol%. As described in an article by Baker in J. Am. Chem. Soc., 2019, 141, 29, 11506, the sole reported product was 1,2-difluorocyclobutene.Examples 99-104, Hydrodefluorination of 1,1,1,4,4,4-Hexafluorobutene (1336mzz; C4F6H2)

[0120] Example 99 was conducted on a —0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, copper (II) naphthenate (Cu(Nap)2; -10 mg, -0.012 mmol, -10 mol%), trimethylphosphite (P(OMe)s; -4.6 mg, -0.037 mmol, -30 mol%), 1,1,3,3-tetramethyldisilane (TMDS) (-1.5 equivalents, -0.185 mmol, -24 mg), and chilled 1336mzz (-0.123 mmol, -20.2 mg) were added and diluted with toluene to -600 pL. In this Example, the concentration ratio of mmol of reactant per mL of solvent was -0.175 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap. Reaction temperature was room temperature (~17-23°C), and the reaction was run for -16 hours. Reaction progress was monitored using19F NMR on a 500 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR without any internal reference standards. In this case, conversion was calculated to be -100% (essentially complete), with products being -100% 1,1,4,4,4-pentafluoro-1-butene (1345czf), -0% Z- 1,4, 4, 4-tetrafluoro-l -butene (Z-1354zef), and -0% E-l, 4,4,4-tetrafluoro-1 -butene (E-1354zef). See the reaction scheme below.

[0121] Example 100 is identical to Example 99, except that the TMDS concentration was increased from -1.5 equivalents to -4.0 equivalents and that the reaction temperature was increased to ~50°C. In this case, conversion was calculated to be -100% (essentially complete), with products being -100% 1,1,4,4,4-pentafluoro-l-butene (1345czf), -0% Z- 1,4,4, 4-tetrafluoro-1 -butene (Z-1354zef), and -0% E-l, 4, 4, 4-tetrafluoro-l -butene (E-1354zef).

[0122] Example 101 is identical to Example 99, except that the TMDS concentration was increased from -1.5 equivalents to -2.0 equivalents and that the P(OMe)s ligand additive was replaced by l,2-bis(diphenylphosphino)ethane (DPPE) with the concentration being reduced to -10 mol%. In this case, conversion was calculated to be -100% (essentially complete), with products being -94% 1,1,4,4,4-pentafluoro-l-butene (1345czf), -4% Z- 1,4, 4, 4-tetrafluoro-l -butene (Z-1354zef), and -2% E-l, 4, 4, 4-tetrafluoro-l -butene (E-1354zef).

[0123] Example 102 is identical to Example 101, except that the TMDS concentration was doubled to -4.0 equivalents and that the reaction temperature was increased to ~80°C. In this case, conversion was calculated to be -100% (essentially complete), with products being -25%1,1,4,4,4-pentafluoro-l-butene (1345czf), -50% Z- 1,4, 4, 4-tetrafluoro-l -butene (Z-1354zef), and -25% E- 1,4, 4, 4-tetrafluoro-l -butene (E-1354zef).

[0124] Comparative Example 103 is identical to Example 102, except that the Cu(Nap)2 catalyst was replaced by Stryker’s catalyst (CuHPPhi as formula, but represented *6 as bipyramidal copper complex) at the same concentration of -10 mol%. In addition, the DPPE ligand additive was replaced by bis(2-dicyclohexylphosphinophenyl)ether (DCEphos) at the same concentration of -10 mol%. In this case, conversion was calculated to be -99% (essentially complete), with products being -4% 1,1,4,4,4-pentafluoro-l-butene (1345czf), -73% Z- 1,4, 4, 4-tetrafluoro-l -butene (Z-1354zef), and -22% E- 1,4, 4, 4-tetrafluoro-l -butene (E-1354zef).

[0125] Example 104 was identical to Example 99 except that it was performed on a -50 mmol scale in a -350 mL pressure tube, and the concentration ratio of mmol of reactant per mL of solvent was -5 Molar. Because of the scale of the reaction, the pressure tube was placed behind a blast shield for -16 hours. Distillation under atmospheric pressure after combining the products from 3 runs resulted in 55% isolated material (-82.5 mmol, -12.04 g) of solely 1345czf (boiling point ~20-23°C).Examples 105-109. Hydrodefluorination of Perfluorocyclopentene (PFCP;

[0126] Example 105 was conducted on a -0.25 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, copper (II) 2-ethylhexanoate (Cu(EH)2) (-9.3 mg, -0.025 mmol, -10 mol%) trimethylphosphite (P(OMe)j) (-9.3 mg, -0.075 mmol, -30 mol%), triethylsilane (-4 equivalents, -1 mmol, -116 mg), PFCP (-0.25 mmol, -53 mg), and cyclopentyl methyl ether (CPME; -0.4 mL) were added. In this Example, the concentration ratio of mmol of reactant per mL of solvent was -0.625 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap. Reaction temperature was room temperature (~17-23°C), and the reaction was run for -20 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR without any internal reference standards. In this case, conversion was calculated to be -50%, with products being -50% cl427yz, -0% cl436zz, and -0% cl445yzf See the reaction scheme below.

[0127] Example 106 is identical to Example 105, except that the triethylsilane (EtaSiH) is replaced by 1,1, 3, 3 -tetramethyl di si lane (TMDS) at an increased concentration representing ~15 equivalents and that the reaction time was reduced to -16 hours. In addition, the CPME solvent was not added, such that this reaction proceeded with substantially no solvent. In this case, conversion was calculated to be -100% (essentially complete), with products being -0% cl427yz, -0% cl436zz, and -100% (essentially all) cl445yzf.

[0128] Example 107 is identical to Example 106, except that the catalyst and ligand additive concentrations were each reduced by 1 / 4 to -2.5 mol% catalyst and -7.5 mol% catalyst, respectively. In this case, conversion was calculated to be -100% (essentially complete), with products being -8% cl427yz, -92% cl436zz, and -0% (essentially all) cl445yzf.

[0129] Example 108 was conducted on a -125 mmol scale. To a -350 mL pressure tube in a nitrogen-filled glovebox, copper (II) 2-ethylhexanoate (Cu(EH)2) (-496 mg, -1.25 mmol, -1 mol%) trimethylphosphite (P(OMe)s) (-465 mg, -3.75 mmol, -3 mol%), polymethylhydrosiloxane (PMHS; -1.07 equivalents, -134 mmol, -8.00 g), and p-xylene (-40 mL) were added, and the reaction vessel was cooled down to — 78°C in a cold well. Then, PFCP (-125 mmol, -26.5 g) was added to the reaction mixture. In this Example, the concentration ratio of mmol of reactant per mL of solvent was -3.0 Molar. The tube was capped, removed from the glovebox, and placed in an ice bath behind a blast shield for -12 hours at room temperature (-17-23°C). The vessel was then brought back to the glovebox, cooled down, and sampled using19F NMR on a 500 MHz Bruker Avance III™ instrument, with conversions were calculated based on the relative integration of signals in19F NMR. In this case, conversion was -100% (essentially complete). Distillation under atmospheric pressure after combining the products from 4 runs resulted in -65-70% isolated yield (-350 mmol, -67.9 g) of cl427yz (boiling point ~44-47°C) as sole observed product.

[0130] Example 109 was conducted on a -125 mmol scale. To a -350 mL pressure tube in a nitrogen-filled glovebox, copper (II) 2-ethylhexanoate (Cu(EH)2) (-496 mg, -1.25 mmol, -1 mol%) trimethylphosphite (P(OMe)a) (-465 mg, -3.75 mmol, -3 mol%),polymethylhydrosiloxane (PMHS; -1.07 equivalents, -134 mmol, -8.00 g), and kerosene (-40 mL) were added, and the reaction vessel was cooled down to — 78°C in a cold well. Then, PFCP (-125 mmol, -26.5 g) was added to the reaction mixture. In this Example, the concentration ratio of mmol of reactant per mL of solvent was -3.0 Molar. The tube was capped, removed from the glovebox, and placed in an ice bath behind a blast shield for -12 hours at room temperature (-17-23°C). The vessel was then brought back to the glovebox, cooled down, and sampled using19F NMR on a 500 MHz Bruker Avance III™ instrument, with conversions were calculated based on the relative integration of signals in19F NMR. The sampling procedure in the glovebox was repeated 3 more times (for a total of 4 catalyst / ligand additive / silane loadings at Oh, 12h, 24h, and 36h; overall catalyst amount added up to -4 mol%). In this case, conversion was -100% (essentially complete). Distillation under atmospheric pressure on products of 4 runs resulted in -40-45% isolated yield (-225 mmol, -43.65g) of cl445yzf in (boiling point ~86-89°C) as the sole observed product.Examples 110-111, Hydrodefluorination of Perfluoro(Methyl Vinyl Ether) (PMVE; C3F6O)

[0131] Example 110 was conducted on a -0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, chromium (III) 2-ethylhexanoate (Cr(EH)s; -7.0 mg, -0.025 mmol, -10 mol%), trimethylphosphite (P(OMe)s; -4.6 mg, -0.037 mmol, -30 mol%), 1,1,3,3-tetramethyldisilane (TMDS) (-1 equivalents, -0.123 mmol, -16.5 mg), and PMVE (-0.123 mmol, -3.0 mL) were added, with dilution of -600 pL of benzene (CeDe) as a solvent. In this Example, the concentration ratio of reactant to solvent was -0.205 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafdm around the cap. Reaction temperature was ~65°C, and the reaction was run for -16 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrument at room temperature (~17-23°C), and conversions were calculated based on the relative integration of signals in19F NMR, without any internal reference standards. In this case, conversion was calculated at -75%, with products being about half each of E- and Z- enantiomers of 1,2-difluoro-l-(trifluoromethoxy)ethene. See the reaction scheme below.

[0132] Example 111 was identical to Example 110, except that the reaction time was extended to ~40 hours. In this case, -100% (essentially complete) conversion was observed, with products being -51% E-l,2-difluoro-l-(trifluorom ethoxy )ethene and -49% Z-l,2-difluoro-l-(trifluoromethoxy)ethene.Examples 112-113, Hydrodefluorination of 3,3, 3 -Trifluoropropene (TFP / 1243zf; C3F3H3)

[0133] Example 112 was conducted on a -0.123 mmol scale (~3mL gaseous). To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, copper (II) naphthenate (Cu(Nap) ; -9.3 mg, -0.0123 mmol, -10 mol%), trimethylphosphite (P(OMe)3, -4.6 mg, -0.037 mmol, -30 mol%), 1,1,3,3-tetramethyldisilane (TMDS) (-1 equivalent, -0.123 mmol, -16.5 mg), and 1243zf (-0.123 mmol, -3 mb) were added, with dilution by -0.6 m of benzene as a solvent. In this Example, the concentration ratio of reactant to solvent was -0.205 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap. Reaction temperature was room temperature (~17-23°C), and the reaction was run for -16 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR, without any internal reference standards. In this case, -92% conversion to 1,1-difluoropropene (1252zc) was observed.

[0134] Example 113 was identical to Example 112, except that P(OMe)s ligand additive was replaced by methyldiphenylphosphine (PMePli2) at the same concentration of -30 mol%. In this case, -93% conversion to 1 , 1 -difluoropropene (1252zc) was observed.Example 114, Hydrodefluorination of 1,2,3,3,3-Pentafluoro-l-Propene (1225ye; C3F5H)

[0135] Example 114 was conducted on a -0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, copper (II) naphthenate (Cu(Nap)2; -4.7 mg, -0.006 mmol, -5 mol%), trimethylphosphite (P(OMe)3; -2.4 mg, -0.018 mmol, -15 mol%), 1,1,3,3-tetramethyldisilane (TMDS) (-1 equivalent, -0.123 mmol, -16.5 mg), and 1225ye (-0.123 mmol, -3 mb) were added, with dilution by -0.6 mb of benzene as a solvent. In this Example, the concentration ratio of reactant to solvent was -0.205 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap. Reaction temperature was room temperature (~17-23°C), and the reaction was run for -16 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrument, andconversions were calculated based on the relative integration of signals in19F NMR. In this case, -70% conversion to 2,3,3,3-tetrafluoropropene (1234yf) was observed.Example 115. Hydrodefluorination of 1,3,3,3-Tetrafluoro-l-Propene (1234ze; C3F4H2)

[0136] Example 115 was conducted on a -0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, copper (II) naphthenate (Cu(Nap)2; -9.3 mg, -0.0123 mmol, -10 mol%), trimethylphosphite (P(OMe)s; -4.6 mg, -0.037 mmol, -30 mol%), 1,1,3,3-tetramethyldisilane (TMDS) (-1 equivalent, -0.123 mmol, -16.5 mg), and 1234ze (-0.123 mmol, -3 mL) were added, with dilution by -0.6 mL of m-xylene as a solvent. In this Example, the concentration ratio of reactant to solvent was -0.205 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap. Reaction temperature was ~80°C, and the reaction was run for -16 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR, without any internal reference standards. In this case, -73% conversion to 1,1 -difluoro- 1 -propene (1252zc) was observed.Example 116. Hydrodefluorination of 1,3,3,3-Tetrafluoro-l-Propene (1233zd; C3F3CIH2)

[0137] Example 116 was conducted on a -0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, copper (II) naphthenate (Cu(Nap)2; -9.3 mg, -0.0123 mmol, -10 mol%), methyldiphenylphosphine (PMePh2; -7.4 mg, -0.037 mmol, -30 mol%), 1,1,3,3-tetramethyldisilane (TMDS) (-1 equivalent, -0.123 mmol, -16.5 mg), and chilled 1233zd (-0.123 mmol, -16.0 mg) were added, with dilution by -0.7 mL of m-xylene as a solvent. In this Example, the concentration ratio of reactant to solvent was -0.175 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap. Reaction temperature was ~80°C, and the reaction was run for -16 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR. In this case, -0% (essentially no) conversion was observed.Examples 117-123. Hydrodefluorination of l,LL2,4,4,4-Heptafluoro-2-Butene (1327myz;

[0138] Example 117 was conducted on a -0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, copper (II) naphthenate (Cu(Nap)2; -9.3 mg, -0.0123 mmol, -10 mol%), trimethylphosphite (P(OMe)s; -4.7 mg, -0.037 mmol, -30 mol%),1,1, 3 ,3 -tetramethyl di si lane (TMDS) (-1 equivalent, -0.123 mmol, -16.5 mg), and 1327myz (-0.123 mmol, 22.4 mg) were added, with dilution by -0.6 mL of toluene as a solvent. In this Example, the concentration ratio of reactant to solvent was -0.175 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafdm around the cap. Reaction temperature was ~80°C, and the reaction was run for -16 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR. In this case, conversion was calculated to be -47%, with products being -43% E-l,l,l,4,4,4-hexafluoro-2-butene (E-1336mzz), -4% 1,1,4,4,4-pentafluoro-l-butene (1345czf), -0% Z- 1,4, 4, 4-tetrafluoro-l -butene, and -0% E- 1,4, 4, 4-tetrafluoro-l -butene. See reaction scheme below.

[0139] Example 118 was identical to Example 117, except that P(OMe)s ligand additive was replaced by l,2-bis(diphenylphosphino)ethane (DPPE) at a reduced concentration of -10 mol%. In this case, conversion was calculated to be -100% (essentially complete), with products being -0% E-l,l,l,4,4,4-hexafluoro-2-butene (E-1336mzz), -65% 1,1,4,4,4-pentafluoro-l-butene (1345czf), -22% Z- 1,4, 4, 4-tetrafluoro-l -butene, and -13% E- 1,4, 4, 4-tetrafluoro-l -butene.

[0140] Example 119 was identical to Example 118, except that the Cu(Nap)2 catalyst was replaced by copper (II) 2-ethylhexanoate (Cu(EH)2) at the same concentration of -10 mol% and that the reaction temperature was increased to ~50°C. In this case, conversion was calculated to be -100% (essentially complete), with products being -0% E-l,l,l,4,4,4-hexafluoro-2-butene (E-1336mzz), -63% 1,1,4,4,4-pentafluoro-l-butene (1345czf), -27% Z- 1,4, 4, 4-tetrafluoro-l -butene, and -10% E-l,4,4,4-tetrafluoro-l-butene.

[0141] Example 120 was identical to Example 118, except that the TMDS concentration was increased to -1.2 equivalents and that the reaction time was decreased to -1.5 hours. In this case, conversion was calculated to be -99% (essentially complete), with products being -0% E-l,l,l,4,4,4-hexafluoro-2-butene (E-1336mzz), -77% 1,1,4,4,4-pentafluoro-l-butene (1345czf), -16% Z- 1,4, 4, 4-tetrafluoro-l -butene, and -6% E- 1,4, 4, 4-tetrafluoro-l -butene.

[0142] Example 121 was identical to Example 120, except that the reaction temperature was increased to ~80°C and the reaction time increased to -22 hours. In this case, conversion wascalculated to be -100% (essentially complete), with products bei ng ~0%E- 1,1, 1,4,4, 4-hexafluoro-2 -butene (E-1336mzz), -39% 1,1,4,4,4-pentafluoro-l-butene (1345czf), -35% Z-l, 4,4,4-tetrafluoro-1 -butene, and -26% E- 1,4,4, 4-tetrafluoro-l -butene.

[0143] Example 122 was identical to Example 119, except that the reaction temperature was increased to ~60°C and the reaction time decreased to -1 hour. In this case, conversion was calculated to be -63%, with products being -23% E-l,l,l,4,4,4-hexafluoro-2-butene (E-1336mzz), -40% 1,1,4,4,4-pentafluoro-l-butene (1345czf), -0% Z-l, 4, 4, 4-tetrafluoro-l -butene, and -0% E- 1,4, 4, 4-tetrafluoro-l -butene.

[0144] Example 123 was identical to Example 118, except that the TMDS concentration was decreased to -0.5 equivalents and that the toluene solvent was removed, such that this reaction proceeded with substantially no solvent. In this case, conversion was calculated to be -45%, with products being -0% E-l,l,l,4,4,4-hexafluoro-2-butene (E-1336mzz), -45% 1,1,4,4,4-pentafluoro-l-butene (1345czf), -0% Z-l, 4, 4, 4-tetrafluoro-l -butene, and -0% E-1,4,4,4-tetrafluoro- 1 -butene.Examples 124-127. Hydrodefluorination of Hexafluoro-1,3-Butadiene (HFBD / 2316;

[0145] Example 124 was conducted on a -0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, chromium (III) 2-ethylhexanoate (Cr(EH)s; -14.0 mg, -0.025 mmol, -20 mol%), trimethylphosphite (P(OMe)s; -9.2 mg, -0.074 mmol, -60 mol%), 1,1,3,3-tetramethyldisilane (TMDS) (-0.5 equivalents, -0.062 mmol, -8.3 mg), and 2316 (-0.123 mmol, -3 mL) were added, with dilution by -0.6 mL m-xylene as a solvent. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap. Reaction temperature was ~80°C, and the reaction was run for -60 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR. In this case, conversion was calculated to be -20%, with products being -20% 1, 1,2,3, 4-pentafluoro- 1,3-butadiene (terminal E-PFBD mono-enantiomer), -0% l,l,2,3,4-pentafluoro-l,3-butadiene (terminal Z-PFBD mono-enantiomer), -0% 1,2, 3, 4-tetrafluoro-l, 3-butadiene (syndiotactic terminal TFBD di-enantiomer), and -0% 1,2, 3, 4-tetrafluoro-l, 3-butadiene (isotactic terminal TFBD di-enantiomer). See reaction scheme below.

[0146] Example 125 is identical to Example 124, except that: the Cr(EH)s catalyst was replaced by copper (II) naphthenate (Cu(Nap)2) at half the concentration, i.e., -10 mol%; the P(0Me)3 ligand additive was replaced by P,P,P',P'-Tetramethyl-P,P'-(9,9-dimethyl-9H-xanthene-4,5-diyl)bis[phosphonite] (Xant(POMe2)2) also at a reduced concentration of -10 mol%; the TMDS concentration was doubled to -1 equivalent; the reaction temperature was reduced to room temperature (~17-23°C); and the reaction time was decreased to -3 hours. In this case, conversion was calculated to be -34%, with products being -25% l,l,2,3,4-pentafluoro-l,3-butadiene (terminal E-PFBD mono-enantiomer), -7% l,l,2,3,4-pentafluoro-l,3-butadiene (terminal Z-PFBD mono-enantiomer), -2% l,2,3,4-tetrafluoro-l,3-butadiene (syndiotactic terminal PFBD dienantiomer), and -0% l,2,3,4-tetrafluoro-l,3-butadiene (isotactic terminal PFBD di-enantiomer).

[0147] Example 126 is identical to Example 125, except that the Xant(POMe2)2 ligand additive was replaced by l,2-bis(diphenylphosphino)ethane (DPPE) at the same concentration of -10 mol%, that the TMDS concentration was doubled to -2 equivalents, and that the reaction time was increased to -16 hours. In this case, conversion was calculated to be -28%, with products being -15% 1,1, 2, 3, 4-pentafluoro- 1,3 -butadiene (terminal E-PFBD mono-enantiomer), -7% 1, 1,2, 3,4-pentafluoro-l,3-butadiene (terminal Z-PFBD mono-enantiomer), -6% l,2,3,4-tetrafluoro-l,3-butadiene (syndiotactic terminal PFBD di-enantiomer), and -0% l,2,3,4-tetrafluoro-l,3-butadiene (isotactic terminal PFBD di-enantiomer).

[0148] Example 127 is identical to Example 126, except that the reaction temperature was increased to ~80°C and the reaction time was decreased to -1 hour. In this case, conversion was calculated to be -76%, with products being -18% l,l,2,3,4-pentafluoro-l,3-butadiene (terminal E-PFBD mono-enantiomer), -4% 1,1, 2, 3, 4-pentafluoro- 1,3 -butadiene (terminal Z-PFBD monoenantiomer), -27% l,2,3,4-tetrafluoro-l,3-butadiene (syndiotactic terminal PFBD di-enantiomer), and -27% l,2,3,4-tetrafluoro-l,3-butadiene (isotactic terminal PFBD di-enantiomer).Examples 128-142, Hydrodefluorination of 1.1 ,1 ,3,4,4,5,5,5-Nonafluoro-2-pentene (2HNF2P / 1429mzy; C5F9H)

[0149] Example 128 was conducted on a -0.1 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, copper (II) naphthenate (Cu(Nap)2; ~9.3 mg, -0.0123 mmol, -10 mol%), trimethylphosphite (P(OMe)3; -4.6 mg, -0.037 mmol, -30 mol%), triethylsilane (EtsSiH) (-1 equivalent, -0.123 mmol, -14.3 mg), and 1429mzy (-0.123 mmol, -28.5 mg) were added, with dilution by -0.6 mb of m-xylene as a solvent. Although represented simply as “1429mzy” in the ingredient list herein, it should be understood that the reactant was actually believed to be a mixture of -90-95% l,l,l,3,4,4,5,5,5-Nonafluoro-2-pentenewith~5-10% of l,l,l,2,4,4,5,5,5-Nonafluoro-2-pentene “impurity”. In this Example, the concentration ratio of reactant to solvent was -0.205 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap. Reaction temperature was ~80°C, and the reaction was run for -24 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR. Where applicable, the tube was immersed upright to the solvent level in a heating bath filled with aluminum beads from Lab Armor (Irving, TX) at the temperature noted for the specified period of time before analysis. In this case, majority-reactant conversion was calculated to be -37%, with non-impurity products being -33% 1,1, 1,4, 4,5,5, 5-octafluoro-2-pentene (1438mzz - enantiomers presumed but not resolved) and -4% 1, 1,1, 2,5,5, 5-heptafluoro-2 -pentene (1447myzf- enantiomers presumed but not resolved). See reaction scheme below.

[0150] Example 129 was identical to Example 128, except that: the P(OMe)a ligand additive was replaced by l,2-bis(diphenylphosphino)ethane (DPPE) at a reduced concentration of -10 mol%; the EtsSiH concentration was doubled to -2 equivalents; and the reaction time was decreased to -3 hours. In this case, majority -reactant conversion was calculated to be -17%, with non-impurity products being -0% l,l,l,4,4,5,5,5-octafluoro-2-pentene (1438mzz - enantiomerspresumed but not resolved) and -17% l,l,l,2,5,5,5-heptafluoro-2-pentene (1447myzf -enantiomers presumed but not resolved).

[0151] Example 130 was identical to Example 129, except that the reaction temperature was decreased to room temperature (~17-23°C) and the reaction time was further decreased to -2 hours. In this case, -0% (essentially no) conversion was observed.

[0152] Example 131 was identical to Example 129, except that the EtaSiH silane was replaced by 1,1,3,3-tetramethyldisilane (TMDS) at a reduced concentration representing -0.5 equivalents. In this case, majority -reactant conversion was calculated to be -37%, with non-impurity products being -0% l,l,l,4,4,5,5,5-octafluoro-2-pentene (1438mzz - enantiomers presumed but not resolved) and -37% l,l,l,2,5,5,5-heptafluoro-2-pentene (1447myzf- enantiomers presumed but not resolved).

[0153] Example 132 was identical to Example 130, except that the EtsSiH silane was replaced by 1,1,3,3-tetramethyldisilane (TMDS) at a reduced concentration representing -0.5 equivalents. In this case, -0% (essentially no) conversion was observed.

[0154] Example 133 was identical to Example 132, except that the DPPE ligand additive was replaced by 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos) at the same concentration of -10 mol%. In this case, majority-reactant conversion was calculated to be -40%, with non-impurity products being -14% l,l,l,4,4,5,5,5-octafluoro-2-pentene (1438mzz -enantiomers presumed but not resolved) and -26% 1, l,l,2,5,5,5-heptafluoro-2-pentene (1447myzf - enantiomers presumed but not resolved).

[0155] Example 134 was identical to Example 133, except that the reaction time was increased to -16 hours. In this case, majority -reactant conversion was calculated to be -48%, with non-impurity products being -16% l,l,l,4,4,5,5,5-octafluoro-2-pentene (1438mzz - enantiomers presumed but not resolved) and -32% l,l,l,2,5,5,5-heptafluoro-2-pentene (1447myzf -enantiomers presumed but not resolved).

[0156] Example 135 was conducted on a -0.123 mmol scale. To an 8” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, copper (II) naphthenate (Cu(Nap)2; -9.3 mg, -0.0123 mmol, -10 mol%), trimethylphosphite (P(OMe)s; -4.6 mg, -0.037 mmol, -30 mol%), and -0.12 mb of a IM solution of triisopropylsilane (iPnSiH) (-1 equivalent, -0.123 mmol, 19.5 mg) in toluene solvent were added. Then, the NMR tube was immersed upright to the solvent level in a pre-cooled bath filled with aluminum beads at - -30°C, and - 0.12 mL a IM solution of1429mzy in toluene was added to the pre-cooled NMR tube. Additional toluene solvent was added until diluted to ~0.6 mb. Although represented simply as “1429mzy” in the ingredient list herein, it should be understood that the reactant was actually believed to be a mixture of -90-95% 1.1.1.3.4.4.5.5.5-Nonafluoro-2-pentene with -5-10% of l,l,l,2,4,4,5,5,5-Nonafluoro-2-pentene “impurity”. In this Example, the concentration ratio of reactant to solvent was -0.205 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap to ensure a tight fit. Reaction temperature was ~80°C, and the reaction was run for -24 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR. Where applicable, the tube was immersed upright to the solvent level in a heating bath filled with aluminum beads from Lab Armor (Irving, TX) at the temperature noted for the specified period of time before analysis. In this case, -0% (essentially no) conversion was observed.

[0157] Example 136 was identical to Example 135, except that the iPnSiH silane was replaced by triethylsilane (EtsSiH) at the same concentration representing -1 equivalent. In this case, majority -reactant conversion was calculated to be -37%, with non-impurity products being -33% 1.1.1.4.4.5.5.5-octafluoro-2-pentene (1438mzz - enantiomers presumed but not resolved) and -4% l,l,l,2,5,5,5-heptafluoro-2-pentene (1447myzf- enantiomers presumed but not resolved).

[0158] Example 137 was identical to Example 136, except that the Cu(Nap)2 catalyst was replaced by copper (II) 2-ethylhexanoate (Cu(EH)2) at the same concentration of -30 mol% and that the reaction time was reduced to -6 hours. In this case, majority-reactant conversion was calculated to be -30%, with non-impurity products being -21% 1,1, 1,4, 4,5,5, 5-octafluoro-2-pentene (1438mzz - enantiomers presumed but not resolved) and -9% 1,1,1,2,5,5,5-heptafluoro-2-pentene (1447myzf- enantiomers presumed but not resolved).

[0159] Example 138 was identical to Example 136, except that the EtsSiH silane was replaced by 1,1,3,3-tetramethyldisilane (TMDS) at the same concentration representing -1 equivalent, that the reaction temperature was reduced to room temperature (~17-23°C), and that the reaction time was reduced to -16 hours. In this case, majority-reactant conversion was calculated to be -94%, with non-impurity products being -39% l,l,l,4,4,5,5,5-octafluoro-2-pentene (1438mzz -enantiomers presumed but not resolved) and -55% 1, l,l,2,5,5,5-heptafluoro-2-pentene (1447myzf - enantiomers presumed but not resolved).

[0160] Example 139 was identical to Example 138, except that the TMDS concentration was reduced to ~0.5 equivalents. In this case, majority -reactant conversion was calculated to be -46%, with non-impurity products being -38% l,l,l,4,4,5,5,5-octafluoro-2-pentene (1438mzz -enantiomers presumed but not resolved) and -8% l,l,l,2,5,5,5-heptafluoro-2-pentene (1447myzf - enantiomers presumed but not resolved).

[0161] Example 140 was identical to Example 139, except that the TMDS concentration was reduced to -0.4 equivalents. In this case, majority -reactant conversion was calculated to be -19%, with non-impurity products being -18% l,l,l,4,4,5,5,5-octafluoro-2-pentene (1438mzz -enantiomers presumed but not resolved) and -1% l,l,l,2,5,5,5-heptafluoro-2-pentene (1447myzf - enantiomers presumed but not resolved).

[0162] Comparative Example 141 was identical to Example 136, except that the Cu(Nap)2 catalyst was replaced by Stryker’s catalyst (CuHPPhs as formula, but represented *6 as bipyramidal copper complex) at a reduced concentration of -10 mol%. In addition, the EESiH silane concentration was increased to represent -1.5 equivalents, the reaction temperature was reduced to room temperature (~17-23°C), and the reaction time was reduced to -1 hour. In this case, significant majority-reactant conversion yielded the sole non-impurity product of 1,1, 1,2, 5, 5, 5 -heptafluoro-2-pentene ( 1447myzf).

[0163] Example 142 was conducted on a -110 mmol scale. To a -350 m pressure tube in a nitrogen-filled glovebox, copper (II) naphthenate (CufNap) ) (-4.365 g, -5.5 mmol, -5 mol%) trimethylphosphite (P(OMe)i) (-2.05 g, -16.5 mmol, -15 mol%), 1,1,3,3-tetramethyldisilane (TMDS; -1 equivalent, -110 mmol, -14.773 g), and p-xylene (-50 mL) were added, and the reaction vessel was cooled down to — 78°C in a cold well. Then, 1429mzy (-110 mmol, -25.53 g) was added to the reaction mixture. In this Example, the concentration ratio of mmol of reactant per mL of solvent was -2.2 Molar. The tube was capped, removed from the glovebox, and placed in an ice bath behind a blast shield for -12 hours at room temperature (~17-23°C). The vessel was then brought back to the glovebox, cooled down, and sampled using19F NMR on a 300 MHz Bruker Avance III™ instrument, with conversions were calculated based on the relative integration of signals in19F NMR. A recharge of the same amount of catalyst, ligand additive, and silane was accomplished at the 12-hour mark, and the reaction was allowed to proceed as above for another -12 hours (-24 hours total). The sampling procedure in the glovebox was repeated with substantially full consumption of reactant. Distillation under atmospheric pressure onproducts of the 2 runs resulted in -63% isolated yield (-140 mmol, -27.4 g) of 1447myzf (boiling point ~30-35°C) as the sole observed non-impurity product. The isolated material contained 5-7% of side products due to the not fully pure nature of starting material (as noted hereinabove, which could have affected the boiling point).Examples 143-144. Hydrodefluorination of Perfluoro(4-Methyl-2 -Pentene) (F-4M2P; CeF )

[0164] Example 143 was conducted on a -0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-fdled glovebox, copper (II) naphthenate (Cu(Nap)2; -9.3 mg, -0.0123 mmol, -10 mol%), l,2-bis(diphenylphosphino)ethane (DPPE; -4.9 mg, -0.0123 mmol, -10 mol%), 1,1,3,3-tetramethyldisilane (TMDS) (-1 equivalent, -0.123 mmol, -14.0 mg), and F-4M2P (-0.123 mmol, -37.0 mg) were added, with dilution by m-xylene as a solvent. In this Example, the concentration ratio of reactant to solvent was -0.205 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap. Reaction temperature was ~80°C, and the reaction was run for -16 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR. In this case, conversion was calculated to be -47%, with products being -37% 1,1, 1,3, 4,5,5, 5-octafluoro-4-(trifluoromethyl)-2 -pentene (A) and -10% l,l,l,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene (B). See reaction scheme below.

[0165] Example 144 was identical to Example 143, except that the Cu(Nap)2 catalyst was replaced by copper (II) 2-ethylhexanoate (Cu(EH)2) at the same concentration of -10 mol%. In this case, conversion was calculated to be -58%, with products being -45% 1, 1,1, 3, 4, 5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene (A) and -13% 1,1, 1,3, 4,5,5, 5-octafluoro-4-(trifluoromethyl)-2-pentene (B).Examples 145-148. Hydrodefluorination of Perfluoro(2-Methyl-2 -Pentene) (F-2M2P; CeFn)

[0166] Example 145 was conducted on a -0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-fdled glovebox, copper (II) naphthenate (Cu(Nap)2; -9.3 mg, -0.0062 mmol, -5 mol%), trimethylphosphite (P(OMe)a; -9.3 mg, -0.0184 mmol, -15 mol%), 1,1,3,3-tetramethyldisilane (TMDS) (-0.7 equivalents, -0.086 mmol, -11.5 mg), and F-2M2P(-0.123 mmol, -37.0 mg) were added, with dilution by benzene as a solvent. In this Example, the concentration ratio of reactant to solvent was -0.205 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap. Reaction temperature was room temperature (~17-23°C), and the reaction was run for -16 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker Avance III™ instrument, and conversions were calculated based on the relative integration of signals in19F NMR. In this case, conversion was calculated to be -95%, with products being -24% 1,1, 1,4, 4,5,5, 5-octafluoro-2-(trifluoromethyl)-2-pentene (mono-HDF), -31% other CeFnH species (but not mono-HDF; referred to as “mono-unresolved”), -10% l,l,4,4,5,5,5-heptafluoro-2-(trifluoromethyl)-l-pentene (di-HDF), -0% Z-l,4,4,5,5,5-hexafluoro-2-(trifluoromethyl)-l-pentene (tri-HDF-a), -0% E-l,4,4,5,5,5-hexafluoro-2-(trifluoromethyl)-l-pentene (tri-HDF-b), and -0% 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-l -pentene (tetra-HDF). See reaction scheme below.

[0167] Example 146 was identical to Example 145, except that both the Cu(Nap)2 catalyst and P(0Me)3 ligand additive concentrations were doubled to -10 mol% and ~30 mol%, respectively, and the TMDS concentration was increased to represent -1.0 equivalent. In this case, conversion was calculated to be -100% (essentially complete), with products being -0% 1, 1, 1, 4, 4, 5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene (mono-HDF), -0% other CeFnH species (but not mono-HDF; referred to as “mono-unresolved”), -100% l,l,4,4,5,5,5-heptafluoro-2-(trifluoromethyl)-l-pentene (di-HDF), -0% Z-l,4,4,5,5,5-hexafluoro-2-(trifluoromethyl)-l-pentene (tri-HDF-a), -0% E-l,4,4,5,5,5-hexafluoro-2-(trifluoromethyl)-l-pentene (tri-HDF-b), and -0% 4, 4, 5,5,5-pentafluoro-2-(trifluorom ethyl)- 1 -pentene (tetra-HDF).

[0168] Example 147 was identical to Example 146, except that the TMDS concentration was further increased to represent -1.5 equivalents. In this case, conversion was calculated to be -100% (essentially complete), with products being -0% 1,1, 1,4, 4,5,5, 5-octafluoro-2-(trifluoromethyl)-2-pentene (mono-HDF), -0% other C6F12H species (but not mono-HDF; referred to as “mono-unresolved”), -6% l,l,4,4,5,5,5-heptafluoro-2-(trifluoromethyl)-l-pentene (di-HDF), ~39% Z-l,4,4,5,5,5-hexafluoro-2-(trifluoromethyl)-l-pentene (tn-HDF-a), -55% E-l,4,4,5,5,5-hexafluoro-2-(trifluoromethyl)-l-pentene (tri-HDF-b), and ~0% 4,4,5,5,5-pentafluoro-2-(trifluorom ethyl)- 1 -pentene (tetra-HDF).

[0169] Example 148 was identical to Example 147, except that the TMDS concentration was again increased to represent ~2.0 equivalents. In this case, conversion was calculated to be -100% (essentially complete), with products being -0% 1,1, 1,4, 4,5,5, 5-octafluoro-2-(trifluoromethyl)-2-pentene (mono-HDF), -0% other C6F12H species (but not mono-HDF; referred to as “monounresolved”), -0% l,l,4,4,5,5,5-heptafluoro-2-(trifluoromethyl)-l-pentene (di-HDF), -21% Z-l,4,4,5,5,5-hexafluoro-2-(trifluoromethyl)-l-pentene (tri-HDF-a), -45% E-1,4,4,5,5,5-hexafluoro-2-(trifluorom ethyl)- 1 -pentene (tri-HDF-b), and -34% 4,4,5,5,5-pentafluoro-2-(trifluorom ethyl)- 1 -pentene (tetra-HDF).Examples 149-156. Hydrodefluorination of 2,2,3,4,5,5-HexaFluoro-2,5-DiHydroThiophene (HFDHT; C4F6S)

[0170] Example 149 was conducted on a -0.123 mmol scale. To a 7” Nuclear Magnetic Resonance (NMR) tube in a nitrogen-filled glovebox, chromium (III) 2-ethylhexanoate (Cr(EH)s; -3.5 mg, -0.0062 mmol, -5 mol%), triisodecylphosphite (TIDP; -9.3 mg, -0.0184 mmol, -15 mol%), tetramethylhydrosiloxane (TMDS; -1.2 equivalents, -0.148 mmol, -21.0 mg), and HFDHT (-0.123 mmol, -24.0 mg) were added, with dilution to -1 m using m-xylene as a solvent. In this Example, the concentration ratio of reactant to solvent was -0.123 Molar. The tube was capped, removed from the glovebox, and further sealed by wrapping a strip of parafilm around the cap. Reaction temperature was room temperature (~17-23°C), and the reaction was run for -24 hours. Reaction progress was monitored using19F NMR on a 300 MHz Bruker instrument, and conversions were calculated based on the relative integration of signals in19F NMR. In this case, -0% (essentially no) conversion was observed. See reaction scheme below.

[0171] Example 150 was identical to Example 149, except that the reaction temperature was increased to ~55°C, and the reaction time was decreased to -18 hours. In this case, conversion was calculated to be -10%, with products being -10% 2,2,3,5,5-pentafluoro-2,5-dihydrothiophene(mono-HDF), -0% 2,2,5,5-tetrafluoro-2,5-dihydrothiophene (di-HDF), and -0% 2,2,4-trifluoro- 2,5-dihydrothiophene (tri-HDF).

[0172] Example 151 was identical to Example 149, except that both the Cr(EH)3 catalyst and TIDP ligand additive concentrations were doubled to -10 mol% and ~30 mol%, respectively, and that the TMDS concentration was increased to represent -3.0 equivalents. In this case, -0% (essentially no) conversion was observed.

[0173] Example 152 was identical to Example 151, except that the reaction temperature was increased to ~55°C, and the reaction time was decreased to -18 hours. In this case, conversion was calculated to be -17%, with products being -17% 2,2,3,5,5-pentafluoro-2,5-dihydrothiophene (mono-HDF), -0% 2,2,5,5-tetrafluoro-2,5-dihydrothiophene (di-HDF), and -0% 2,2,4-trifluoro- 2.5-dihydrothiophene (tri-HDF).

[0174] Example 153 was identical to Example 149, except that the Cr(EH)a catalyst was replaced by copper (II) naphthene (Cu(Nap)2) at the same concentration of -5 mol%. In this case, conversion was calculated to be -100% (essentially complete), with products being -52% 2.2.3.5.5-pentafluoro-2,5-dihydrothiophene (mono-HDF), -48% 2,2,5,5-tetrafluoro-2,5-dihydrothiophene (di-HDF), and -0% 2,2,4-trifluoro-2,5-dihydrothiophene (tri-HDF).

[0175] Example 154 was identical to Example 153, except that the reaction time was reduced to -3 hours. In this case, conversion was calculated to be -96%, with products being -90% 2, 2, 3,5,5-pentafluoro-2,5-dihydrothiophene (mono-HDF), -6% 2,2,5,5-tetrafluoro-2,5-dihydrothiophene (di-HDF), and -0% 2,2,4-trifluoro-2,5-dihydrothiophene (tri-HDF).

[0176] Example 155 was identical to Example 154, except that both the Cu(Nap)2 catalyst and TIDP ligand additive concentrations were doubled to -10 mol% and -30 mol%, respectively, and that the TMDS concentration was increased to represent -3.0 equivalents. In this case, conversion was calculated to be -100% (essentially complete), with products being -39% 2, 2, 3,5,5-pentafluoro-2,5-dihydrothiophene (mono-HDF), -61% 2,2,5,5-tetrafluoro-2,5-dihydrothiophene (di-HDF), and -0% 2,2,4-trifluoro-2,5-dihydrothiophene (tri-HDF).

[0177] Example 156 was identical to Example 155, except the reaction time was increased to -24 hours. In this case, conversion was calculated to be -100% (essentially complete), with products being -15% 2,2,3,5,5-pentafluoro-2,5-dihydrothiophene (mono-HDF), -71% 2, 2,5,5-tetrafluoro-2,5-dihydrothiophene (di-HDF), and -14% 2,2,4-trifluoro-2,5-dihydrothiophene (tri-HDF).Examples 157-162, Hydrodefluorination and / or Hydrodechlorination of Chlorotrifluoroethylene (CTFE; C2F3C

[0178] Example 157 was identical to Example 87, except that a portion of the Cr(EH)s catalyst was replaced by copper (II) 2-ethylhexanoate (Cu(EH)2) so as to achieve a 2:1 molar ratio of chromium to copper catalyst and so as to triple the overall catalyst concentration to ~30 mol%, with the chromium catalyst thus being present at ~20 mol% and the copper catalyst being present at -10 mol%. In addition, the benzene solvent was replaced by cyclopentyl methyl ether (CPME) at the same volume. In this case, conversion was calculated at -67%, with products being -31% E-l 122a, -36% Z-l 122a, -0% E-l 132, and -0% Z-l 132. See reaction scheme below.

[0179] Examples 158-159 were identical to Example 157, except that the reaction temperatures were decreased to ~50°C (Example 158) and room temperature (~17-23°C; Example 159), respectively. In these cases, conversions were calculated at -13% (Example 158) and -5% (Example 159), with products being: Example 158 — 5% E-l 122a, -8% Z-l 122a, -0% E-l 132, and -0% Z-l 132; and Example 159 - -2% E-l 122a, -3% Z-l 122a, -0% E-l 132, and -0% Z-1132.

[0180] Example 160 was identical to Example 75, except that the Cr(EH)3 catalyst was replaced by copper (II) 2-ethylhexanoate (Cu(EH)2) at the same concentration of -10 mol%. In addition, the benzene solvent was replaced by cyclopentyl methyl ether (CPME) at the same volume, and the reaction temperature was reduced to ~50°C. In this case, conversion was calculated at -10%, with products being -0% E-l 122a, -0% Z-l 122a, -9% E-l 132, and -1% Z-l 132.

[0181] Example 161 was identical to Example 160, except that a portion of the Cu(EH)2 catalyst was replaced by chromium (II) 2-ethylhexanoate (Cr(EH)a) so as to achieve a 2:1 molar ratio of chromium to copper catalyst and so as to triple the overall catalyst concentration to -30 mol%, with the chromium catalyst thus being present at -20 mol% and the copper catalyst being present at -10 mol%. In this case, conversion was calculated at -55%, with products being -22% E-1122a, -25% Z-l 122a, -5% E-l 132, and -3% Z-l 132.

[0182] Example 162 was identical to Example 161, except that the reaction temperature was increased to ~70°C. In this case, conversion was calculated at -100% (essentially complete), with products being -45% E-l 122a, -48% Z-l 122a, -4% E-l 132, and -3% Z-l 132.Example 163. Hydrodefluorination and / or Hydrodechlorination of 1,3,3,3-Tetrafluoro-l-Propene (1233zd; C3F3C1H2)

[0183] Example 163 was identical to Example 116, except that the PMePh2ligand additive was replaced by 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos) at a reduced concentration of -10 mol% and that the reaction temperature was reduced to room temperature (~17-23°C). In this case, conversion was calculated at -15%, with products being -2% 1243zf and -13% 1252zc. See reaction scheme below.Examples 164-165. Robustness in Oxidative Environments of Hydrodefluorination of Perfluoro(2-Methyl-2-Pentene) (F-2M2P; CeF )

[0184] Example 164 was conducted on a -0.636 mmol scale. To a ~20-mL- borosilicate glass vial containing a magnetic stir bar, in an fume hood environment including air, copper (II) naphthenate (Cu(Nap)2; -52.0 mg, -0.0688 mmol, -11 mol%), triisodecylphosphite (TIDP; -92.0 mg, -0.183 mmol, -29 mol%), polymethylhydrosiloxane (PMHS; -2.6 equivalents, -1.65 mmol, -99 mg), and F-2M2P (-0.636 mmol, -191 mg) were added, with dilution to -4.0 mL using o-xylene as a solvent. In this Example, the concentration ratio of reactant to solvent was -0.159 Molar. The vial was capped and placed on a stirring plate. Reaction temperature was room temperature (~17-23°C), and the reaction was run for -18 hours. Reaction progress was assessed using19F NMR on a 300 MHz Bruker instrument, and conversions were calculated based on the relative integration of signals in19F NMR. In this case, conversion was calculated to be -100% (essentially complete), with products being -0% 1,1, 1,4, 4,5,5, 5-octafluoro-2-(trifhioromethyl)-2-pentene (mono-HDF), -0% other CeFi2H species (but not mono-HDF; referred to as “monounresolved”), -50% l,l,4,4,5,5,5-heptafluoro-2-(trifluoromethyl)-l-pentene (di-HDF), -18% Z-l,4,4,5,5,5-hexafluoro-2-(trifluoromethyl)-l-pentene (tri-HDF-a), -32% E-l, 4, 4, 5,5,5-hexafluoro-2-(trifluoromethyl)-l -pentene (tri-HDF-b), and -0% 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)- 1 -pentene (tetra-HDF), with multiple species believed to correspond to copperbased intermediates being present (but normalized out of the conversion calculation).

[0185] Example 165 was identical to Example 164, except that PMHS silane concentration was increased to ~4.0 equivalents. In this case, conversion was calculated to be -100% (essentially complete), with products being -0% l,l,l,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene (mono-HDF), -0% other C6F12H species (but not mono-HDF; referred to as “mono-unresolved”), -0% l,l,4,4,5,5,5-heptafluoro-2-(trifluoromethyl)-l-pentene (di-HDF), -27% Z-1,4,4,5,5,5-hexafluoro-2-(trifluoromethyl)-l -pentene (tri-HDF-a), -54% E-l,4,4,5,5,5-hexafluoro-2- (trifluorom ethyl)- 1 -pentene (tri-HDF-b), and -5% 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-l-pentene (tetra-HDF), with the balance comprising multiple species believed to correspond to copper-based intermediates.

Claims

CLAIMSWhat is claimed is:

1. A process for selectively hydrodehalogenating a halogen-containing unsaturated reactant to form a less-halogenated unsaturated product comprising selectively hydrodehalogenating the halogen-containing unsaturated reactant, by exposing it to a transition metal carboxylate in the presence of a hydride source and also a ligand additive, to form the less-halogenated unsaturated product.

2. The process of claim 1, wherein the reactant comprises from 2 to 12 carbon atoms, e.g., from 2 to 8 carbon atoms, from 2 to 6 carbon atoms, or from 3 to 6 carbon atoms.

3. The process of claim 1 or claim 2, wherein the transition metal carboxylate comprises:a transition metal selected from the group consisting of Ag, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof; anda carboxylate selected from the group consisting of a naphthenate, formate, acetate, a propionate, a butyrate, a pentanoate, a hexanoate, an octanoate, a decanoate, a dodecanoate, a tetradecanoate, a hexadexanoate, an octadecanoate, a tetradecenoate, a hexadecenoate, an octadecenoate, pyrazinecarboxylate, acetylacetonate (Acac), and mixtures thereof.

4. The process of any of claims 1-3, wherein the hydride source comprises a tri(Cl-C6 alkyl)silane, a tetra(Cl-C6 alkyl)disiloxane, a di-(Cl-C6 alkyl) phenylsilane, a (C1-C6 alkyl)diphenylsiloxane, a polysilane, lithium aluminum hydride, or a mixture thereof.

5. The process of any of claims 1-4, wherein the ligand additive comprises a diimidopyridine, a tri(C2-C18 alkyl and / or alkenyl)phosphite, an n,n’-bis(diarylphosphino)alkane, an n,n’,n”-tris(diarylphosphino)alkane, pyridine, a di(Cl-C6 alkyl)aminopyridine, 2,2 ’-bipyridine, 2,2’:6’,2”-terpyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, (S)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole, 2,6-bis[(4S)-4,5-dihydro-4-( l-methylethyl)-2-oxazolyl]pyridine, a methanesulfonate, a monofluoromethanesulfonate, a difluoro-methanesulfonate, a triflate (trifluoromethanesulfonate), triisopropylphosphite, tri(2-ethylhexyl)phosphite, triisodecylphosphite, trioleylphosphite, triphenylphosphite, tritolylphosphite, tris(nonylphenyl)phosphite, 1,2-bis(dicyclohexylphosphino)ethane, l,2-bis(dicyclopentylphosphino)ethane, 1,2-bis(diisobutylphosphino)ethane, l,2-bis(diphenylphosphino)ethane, 1,1’-bi s(diphenylphosphino)ferrocene, bi s(2-di cyclohexylphosphinophenyl)ether, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, P,P,P',P'-tetramethyl P,P'-(9,9-dimethyl-9H-xanthene-4, 5 - diy 1 )b i s [phosphonite], 1,1,1 -tri s(diphenylphosphinomethyl)ethane, bi s [2-(diphenylphosphino)ethyl]phenylphosphine, N,N'-bis(2,6-diisopropylphenyl)ethane-l,2-diimine, or a mixture thereof.

6. The process of any of claims 1-5, wherein the selective hydrodehalogenation is performed in the presence of a solvent comprising benzene, toluene, a xylene (e.g., m-, p-, o-, or a mixture thereof), mesitylene, chlorobenzene, di chlorobenzene e.g., o-DCB), pyridine, dimethyl benzamide, dimethylaniline, anisole, methylcarbazole, methylindole, benzofuran, diphenylether, dibenzyl ether, diglyme, dimethyl acetamide (DMAc), dimethyl formamide (DMF), cyclopentyl methyl ether (CPME), methyl t-butyl ether (MTBE), tetrahydrofuran (THF), formaldehyde, acetaldehyde, acetonitrile, petroleum distillate, petroleum spirits, kerosene, hexane, heptane, octane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, or a mixture thereof.

7. The process of any of claims 1-6, wherein the selective hydrodehalogenation is performed in the substantial absence of triaryl phosphines.

8. The process of any of claims 1-7, wherein the selective hydrodehalogenation is performed at a temperature from 0°C to 150°C, for example from 15°C to 120°C, from 30°C to 110°C, or from 40°C to 100°C.

9. The process of any of claims 1-8, wherein the less-halogenated unsaturated product has a selectivity of at least 50%, at least 60%, at least 70%, at least 80%, at least 85%, or at least 90%.

10. The process of any of claims 1-9, further comprising a step of isolating and / or purifying one or more selective isomeric species, relative to all other products.

11. A composition of formula (E):wherein Ri is F, Cl, CF3, CHF2, or CFH2; each R2 is independently H, F, or Cl, with at least one R2 being H; each R3 is independently H, F, or Cl, with at least one R3 being F; R4 is(CX2) m CX3, with m being 0, 1, or 2, and with each X independently being H or F but with at least one X being F; and n is 0 or 1 or 2.

12. The composition of claim 11, wherein Ri is F, CF3, CHF2, or CFH2; each R2 is independently H or F, with at least one R2being H; both R3 are F; R4 is (CX2)mCX3, with m being 0 or 1, and with each X independently being H or F but with no more than two X’s being H; and n is 0 or 1.

13. The composition of claim 12, wherein Ri is CF3; both R2are H; both R3 are F; R4 is CF3; and n is 0 or 1.

14. The composition of claim 12, wherein Ri is F; both R2 are H; both R3 are F; R4 is CF3; and n is 1.

15. The composition of claim 12, wherein Ri is H; both R2 are F; R4 is CF3; and n is 0.

16. The composition of claim 12, wherein Ri is F; one R2 is F, while the other R2 is H; R4 is CF3; and n is 0.

17. A composition comprising:a non-perhalogenated unsaturated product made by reaction of a transition metal carboxylate and a halogen-containing reactant, the non-perhalogenated unsaturated product comprising at least one fluorine atom and optionally an oxygen or sulfur atom as an ether or thioether, respectively;a transition metal carboxylate and / or a fluorine-substituted transition metal carboxylate compound;a fluorine-substituted hydride compound;a ligand additive; andoptionally an organic solvent.

18. The composition of claim 17, wherein the non-perhalogenated unsaturated product contains from 2 to 8 carbons and is selected from the group consisting of trifluoroethylene, trichloroethylene, fluorodichloroethylene, chlorodifluoroethylene, difluoroethylene, chlorofluoroethylene, hexafluoropropylene, pentafluoropropene, tetrafluoropropene, chlorotrifluoropropene, trifluoropropene, difluoropropene, vinyl fluoride, difluoro-(trifluoromethoxy)ethylene, fluoro-(trifluoromethoxy)ethylene, trifluoromethoxyethene, difluoromethoxyethene, fluoromethoxyethene, pentafluoro- 1,3-butadiene, tetrafluoro- 1,3-butadiene, trifluoro- 1,3 -butadiene, difluoro-l,3-butadiene, perfluorocyclobutene,pentafluorocyclobutene, tetrafluorocyclobutene, tri fluorocyclobutene, difluorocyclobutene, fluorocyclobutene, heptafluorobutene, hexafluorobutene, pentafluorobutene, tetrafluorobutene, trifluorobutene, difluorobutene, fluorobutene, heptafluorocyclopentene, hexafluorocyclopentene, pentafluorocyclopentene, tetrafluorocyclopentene, trifluorocyclopentene, difluorocyclopentene, fluorocyclopentene, nonafluoropentene, octafluoropentene, heptafluoropentene, hexafluoropentene, pentafluoropentene, tetrafluoropentene, trifluoropentene, difluoropentene, hexafluorodihydrothiophene, pentafluorodihydrothiophene, tetrafluorodihydrothiophene, trifluorodihydrothiophene, difluorodihydrothiophene, trifluoromethyl tetrafluoropropenyl ether, and mixtures thereof.

19. The composition of claim 17 or claim 18, wherein the transition metal carboxylate comprises:a transition metal selected from the group consisting of Ag, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof; anda carboxylate selected from the group consisting of a naphthenate, formate, acetate, a propionate, a butyrate, a pentanoate, a hexanoate, an octanoate, a decanoate, a dodecanoate, a tetradecanoate, a hexadexanoate, an octadecanoate, a tetradecenoate, a hexadecenoate, an octadecenoate, pyrazinecarboxylate, acetyl acetonate (Acac), and mixtures thereof.

20. The composition of any of claims 17-19, wherein the fluorine-substituted transition metal carboxylate comprises a transition metal carboxylate in which one of the carboxylate moieties is substituted by a fluorine atom.

21. The composition of any of claims 17-20, wherein the fluorine-substituted hydride compound comprises atri(Cl-C6 alkyl)fhiorosilane, a mono-fluoro-tetra(Cl-C6 alkyl)disiloxane, a difluoro-tetra(Cl-C6 alkyl)disiloxane, a (C1-C6 alkyl)diarylfluorosilane, a di-(C1-C6 alkyl)arylfluorosilane, a mono-, di-, or poly- fluoro-substituted polysilane, a mono-, di-, tri-, or tetra-fluoro-substituted lithium aluminum hydride, or a mixture thereof.

22. The composition of any of claims 17-21, wherein the ligand additive comprises a diimidopyridine, a tri(C2-C18 alkyl and / or alkenyl)phosphite, an n,n’-bis(diarylphosphino)alkane, an n,n’,n”-tris(diarylphosphino)alkane, pyridine, a di(Cl-C6 alkyl)aminopyridine, 2,2’ -bipyridine, 2,2’:6’,2”-terpyridine, 1 , 10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, (S)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole, 2,6-bis[(4S)-4,5-dihydro-4-(l-methylethyl)-2-oxazolyl]pyridine, a methanesulfonate, a monofluoro-methanesulfonate, a difluoro-methanesulfonate, atriflate (trifluoromethanesulfonate), triisopropylphosphite, tri(2-ethylhexyl)phosphite, triisodecylphosphite, trioleylphosphite, triphenylphosphite, tritolylphosphite, tris(nonylphenyl)phosphite, 1,2-bis(dicyclohexylphosphino)ethane, l,2-bis(dicyclopentylphosphino)ethane, 1,2-bis(diisobutylphosphino)ethane, l,2-bis(diphenylphosphino)ethane, 1,1’-bis(diphenylphosphino)ferrocene, bis(2-dicyclohexylphosphinophenyl)ether, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, P,P,P',P'-tetramethyl P,P'-(9,9-dimethyl-9H-xanthene-4, 5 - di y 1 )b i s [phosphonite], 1,1,1 -tri s(dipheny lphosphinomethyl)ethane, bi s [2-(diphenylphosphino)ethyl]phenylphosphine, N,N'-bis(2,6-diisopropylphenyl)ethane-l,2-diimine, or a mixture thereof.

23. The composition of any of claims 17-22, wherein the organic solvent is present and comprises benzene, toluene, a xylene (e.g, m-, p-, o-, or a mixture thereof), mesitylene, chlorobenzene, di chlorobenzene (e.g., o-DCB), pyridine, dimethyl benzamide, dimethylaniline, anisole, methylcarbazole, methylindole, benzofuran, di phenyl ether, dibenzyl ether, diglyme, dimethyl acetamide (DMAc), dimethyl formamide (DMF), cyclopentyl methyl ether (CPME), methyl t-butyl ether (MTBE), tetrahydrofuran (THF), formaldehyde, acetaldehyde, acetonitrile, petroleum distillate, petroleum spirits, kerosene, hexane, heptane, octane, cyclohexane, cycloheptane, cyclooctane, norbomane, adamantane, or a mixture thereof.

24. The process of any of claims 17-23, wherein the composition comprises substantially no tri arylphosphines.