Selective hydrodehalogenation using organophosphines

Abstract

The present disclosure describes selective hydrodehalogenation reactions involving compositions comprising organophosphines and optionally metal- or metalloid- containing Lewis acids under various conditions. Also described are product compositions, and in some cases novel compounds, resulting from such reactions.

Description

SELECTIVE HYDRODEHALOGENATION USING ORGANOPHOSPHINESFIELD

[0001] The present disclosure describes selective hydrodehalogenation reactions involving compositions comprising organophosphines under various conditions. Also described are product compositions, and in some cases novel compounds and / or intermediates, 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 etal.,Nat. Commun., 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 Lewis acids and / or medium(media) / solvent(s). The present disclosure identifies not only catalyst-ligand systems and reaction conditions but also the unexpected yields, performance characteristics, and selectivities to specific intermediates / 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 olefin feedstocks. This nucleophilic hydrodehalogenation does not necessarily require metal hydrides but employs tertiary phosphine compounds as terminal reductants. If desired, the tertiary phosphine can be regenerated by incorporation of a very strong base, e.g., a metalloid hydride source such as a silane, as a terminal reductant to achieve one or more enantiomerically selective products. This can allow the phosphine to be employed even substoichiometrically at relatively high yields.

[0014] Reinforcing the surprising and unexpected aspects of chemistry at times, divergent chemoselectivity can arise in various systems depending on the alkylphosphine used, for example, with P(n-Bu)s selectively yielding CF3CF=CH2 (1234yf) and P(i-Bu)a tending to yield the kinetic isomer of CF3CF=CHF (E-1225ye), using hexafluoropropylene (HFP) as the halogenated reactant. Further, even heteroatom-containing haloolefins can be hydrodehalogenated using phosphines, 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] In addition, certain organometallic or organometalloid Lewis acids e.g., titanium alkoxides / alkyl titanates, boron aryloxides / aryl borates, or the like) can be included in the HDH reactions. Without being bound by theory, it is believed that the certain Lewis acids can activate the (hydride) terminal reductants to reduce any phosphine oxide (undesired) byproducts and / or to regenerate halogenated phosphines formed during the reactions.

[0016] Furthermore, this chemical approach can be used to synthesize unique halophosphoranes and / or less halogenated (though still halogenated) products.DETAILED DESCRIPTION

[0017] 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]”.

[0018] 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 tri substitution), 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 (and trialkyl) phosphine / ligand.

[0019] 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 hydrocarbonaceous compounds / 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 organophosphines 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, hydrogen, and / or halogen atoms (but with halogen atoms only being bonded to the phosphorus atom when one or more hydrogen and / or carbon atoms are also bonded to the phosphorus atom as well - in other words, PF3 is not considered a phosphine herein, but FPH2 and F2PH are both considered phosphines herein and FP(CHs)2 and F2PCH3 are both considered organophosphines herein).

[0020] As used herein and unless otherwise defined, the phrase “[containing / comprising] 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 indicate presence 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.

[0021] 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 broadly include fully saturated carbons (only single bonds - no double or triple bonds, and no aromatic character), it is typically unsaturated and often contains a carboncarbon 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 - the hydrodehalogenation system (catalyst, ligand additive, base / silane, etc.) and / or reaction conditions / severity, among other things, may impact that selectivity.

[0022] 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 2 to 4 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 2 to 4 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-(trifluoromethoxy)ethene, trifluoromethoxy ethene, difluoromethoxyethene, hexafluoro- 1,3 -butadiene (2316), pentafluoro- 1,3 -butadiene, tetrafluoro-1,3 -butadiene, trifluoro- 1,3 -butadiene, difluoro- 1,3 -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.

[0023] The hydrodehalogenating process described herein can include exposing the halogencontaining unsaturated reactant to a (hydrocarbyl) phosphine component in the presence of a (metalloid) hydride source and optionally a (metal- or metalloid- containing) Lewis acid, for a time and at a temperature sufficient to form the halophosphorane intermediate. The halophosphorane intermediate may be a relatively stable (by-)product or may be fleeting (undetectable in meaningful concentrations) or a construct based on a presumed reaction scheme toward an ultimate achievement, via selective hydrodehalogenation reaction, of the less-halogenated unsaturated product. Thus, the recited steps of exposing and selectively hydrodehalogenating, though necessarily occurring “in order,” may represent separate reaction steps, enabling actual isolation of a halophosphorane “product,” or may represent simultaneous or near-simultaneous portions of what appears as essentially a single reaction step. Such near-simultaneous reaction may still yield measurable amounts of a halophosphorane compound, as described herein, even if not practically isolatable / stable during the reaction.

[0024] Advantageously, the (trihydrocarbyl) phosphine component can include, but is not necessarily limited to, a tri(C2-C18 alkyl) phosphine such as a tri(C3-C12 alkyl) phosphine, 1,2-bis(dicyclohexylphosphino)ethane, l,2-bis(dicyclopentylphosphino)ethane, 1,2-bis(diisobutylphosphino)ethane, bis(2-dicyclohexylphosphinophenyl)ether (DCEphos), an n,n’-bis(diarylphosphino)alkane, an n,n’,n”-tris(diarylphosphino)alkane such as 1,1,1-tris(diphenylphosphinomethyl)ethane (Tripod), l,2-bis(diphenylphosphino)ethane (Diphos), 1,1’-bis(diphenylphosphino)ferrocene, bis[2-(diphenylphosphino)ethyl]phenylphosphine (TriPhos), 9-isobutyl-9-phosphabicyclo[3.3.1]nonane; 9-isobutyl-9-phosphabicyclo[4.2.1]nonane; 9-n-butyl-9-phosphabicyclo[3.3.1]nonane; 9-n-butyl-9-phosphabicyclo[4.2.1]nonane; 1,2-bis(diisobutylphosphino)ethane; l,3-bis(diisobutylphosphino)propane; 2-n-butyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-n-hexyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-n-decyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-cyclohexylmethyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-benzyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; and 2-(3-hydroxyl-l-propyl)-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane, or a mixture thereof.

[0025] Advantageously, the hydride source can contain or be a tri(Cl-C6 alkyl)silane (e. , 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. If the hydride source is a metalloid hydride source, the non-limiting examples can therefore include all but lithium aluminum hydride.

[0026] Optionally but typically, the hydrodehalogenation reaction(s) can be performed in the presence of a Lewis acid, e.g., a metal- or metalloid- containing Lewis acid. When a metalcontaining Lewis acid, the metal can advantageously contain or be a transitional metal, such as from one or more of Groups 4, 5, 8, and 10 of the Periodic Table of Elements, in particular comprising Ti, Zr, Fe, Ni, or a combination thereof, or comprising a Group 4 metal, or comprising Ti. When a metalloid-containing Lewis acid, the metalloid can advantageously contain or be boron. In preferred and / or particular embodiments, the Lewis acid can contain substantially no transition metal from any of Groups 6-7, 9, and 11-12 of the Periodic Table of Elements, nor selected from the group consisting of Ag, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof.

[0027] When the optional Lewis acid component is not present, in particular the hydrodehalogenation process (the exposing and selective reaction steps) can be performed in the substantial absence of transition metals, or of metals from Groups 4 and 6-12 of the Periodic Table of Elements. Whether the optional Lewis acid component is present or not, and in particular when it is present, the hydrodehalogenation process (the exposing and selective reaction steps) canadvantageously be performed in the substantial absence of transition metals from Groups 6-7, 9, and 11-12 of the Periodic Table of Elements, such as in the substantial absence of transition metals selected from the group consisting of Ag, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof.

[0028] Optionally but typically, the hydrodehalogenation reaction(s) can be performed in the presence of a solvent, e.g., an organic solvent. Non-limiting examples of organic 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-di oxane, 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). While some may define water as an organic solvent, despite its lack of carbon atoms, the definition of organic solvent herein specifically does not include water. Nevertheless, that is not to say that water itself must be excluded, as it may be present in small amounts in a mixed solvent medium (as a deliberately added co-solvent and / or as an impurity or contaminant in one or more organic solvents / media) - however, because (without being bound by theory) it is believed that water could likely disrupt, if not poison, one or more steps in the overall hydrodehalogenation reaction scheme, water is typically not a preferred (co-)solvent.

[0029] In particular embodiments, whether the (metal- / metalloid- containing) Lewis acid is present or not, the selective hydrodehalogenation reaction (both exposing and selective reaction steps) and / or the composition before, during, and / or after said reaction(s) can be characterized as including: less than 500 wppm of metals from Groups 6-7, 9, and 11-12 of the Periodic Table of Elements; less than 200 wppm of metals from Groups 6-7, 9, and 11-12 of the Periodic Table of Elements that do not originate as impurities from the optional organic solvent; or both. When the metal-containing Lewis acid is not present, in particular, the selective hydrodehalogenation reaction (both exposing and selective reaction steps) and / or the composition before, during, and / orafter said reaction(s) can be characterized as including: less than 500 wppm (e.g, less than 300 wppm) of metals; less than 200 wppm (e.g., less than 100 wppm) of metals that do not originate as impurities from the optional organic solvent; or both. Even when the metalloid-containing Lewis acid is present, in particular, the selective hydrodehalogenation reaction (both exposing and selective reaction steps) and / or the composition before, during, and / or after said reaction(s) can be characterized as including: less than 500 wppm (e.g., less than 300 wppm) of metals; less than 200 wppm e.g., less than 100 wppm) of metals that do not originate as impurities from the optional organic solvent; or both. Also when the (metal - / metalloid- containing) Lewis acid is not present, in particular, the phosphine ligand / component in the selective hydrodehalogenation reaction (both exposing and selective reaction steps) and / or in the composition before, during, and / or after said reaction(s) can comprise, consist essentially of, or be a tri(C3-C6 alkyl) phosphine, for example a tri(C3-C4 alkyl) phosphine such as triisobutylphosphine, tri(n-propyl)phosphine, or tri(n-butyl)phosphine, or for certain selectivities specifically tri(n-butyl)phosphine.

[0030] In various embodiments, the exposure and selective reaction steps of the overall hydrodehalogenation process can each / collectively 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 for exposure and / or selective hydrodehalogenation steps can be chosen (or extended or shortened) to allow sufficient halophosphoranation and / or selective reaction(s) at particular reaction temperature(s) and / or within particular temperature range(s). Additionally or alternatively, the exposure step can be performed at a temperature from ~0°C to ~100°C, for example from ~10°C to ~70°C; the selective reaction step can be performed at a temperature from ~20°C to ~130°C, for example from ~40°C to ~110°C or from ~50°C to ~100°C; or both.

[0031] 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). As such, 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, from 2 to 4 carbon atoms, or from 3 to 6 carbon atoms (in particular, from 2 to 8 carbon atoms, from 2 to 6 carbon atoms, from 2 to 4 carbon atoms, from 3 to 8 carbon atoms, or from 3to 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 halogencontaining 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 heteroatoms are present, an oxygen atom as an ether or a sulfur atom as a thioether).

[0032] Non-limiting examples of less halogenated (non-perhalogenated) products can include, but are not necessarily limited to, trifluoroethylene (1123), chlorodifluoroethylene (1122, 1122a), difluoroethylene (1132, 1132a), chlorofluoroethylene (1131, 1131a), vinyl chloride (1140), hexafluoropropylene, pentafluoropropene (1225ye), tetrafluoropropene (1224yf, 1234ze), chlorotrifluoropropene (1233zd, 1233xf), trifluoropropene (1243zf), difluoropropene (1252zc), vinyl fluoride (1141), difluoro-(trifluoromethoxy)ethene, fluoro-(trifluoromethoxy)ethene, trifluoromethoxy ethene, difluoromethoxy ethene, fluoromethoxy ethene, pentafluoro- 1,3-butadiene, tetrafluoro- 1,3 -butadiene, trifluoro- 1,3 -butadiene, difluoro-l,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, hexafluorodihydrothiophene (e.g., 2,2,3,4,5,5-hexafluoro-2,5-dihydrothiophene), pentafluorodihydrothiophene, tetrafluorodihydrothiophene, trifluorodihydrothiophene, difluorodihydrothiophene, trifluoromethyl tetrafluoropropenyl ether, and the like, and mixtures thereof.

[0033] 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 anyunreacted reactant nor any phosphine, whether consumed or not, nor any Lewis acid 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-purifi cation step on the reactant composition.

[0034] Without being bound by theory, it is believed that the reaction between the phosphine component and the halogen-containing (unsaturated) reactant seems to proceed without assistance to effectively insert itself between a carbon of the halogen-containing reactant (typically, but not always, one carbon of the carbon-carbon double bond) and a halogen attached to that carbon to thereby form a halophosphorane intermediate, which halophosphorane may or may not be stable at conditions within the reactor / vessel. Then, when the Lewis acid component is not present, it is believed that the hydride source may add a hydrogen atom to the intermediate, such as to the phosphorus atom thereof, thereby enabling the phosphorus-containing moiety to be a more labile leaving group. When the Lewis acid component is present, it can mediate the hydriding of the halophosphorane intermediate, in concert with the hydride source. Whether in an apparent single step or through a stable or semi-stable halophosphorane intermediate, a selective departure of the phosphorus-containing moiety containing the halogen previously proximate to the carbon to which the phosphorus is complexed / attached to liberate the halogen-containing phosphorus moiety but leaving a hydrogen on the carbon previously containing the halogen thereby completes the selective hydrodehalogenation. The phosphorus-containing leaving group (or the Lewis acid, if present) can react with the hydride source to remove the halogen and to regenerate the phosphine component (or the Lewis acid, as appropriate), thereby forming the fluorosubstituted hydride source. Alternatively, instead of a “fresh” (or regenerated) trihydrocarbyl phosphine, a halided but unregenerated halophosphorane can react with another halogen-containing reactant similarly, but with one of the “ligands” on the phosphorus being a halogen while the other ligands are hydrocarbyl groups - the leaving group in that case is a doubly halide halophosphorane, which is believed to be either very slow to react a third time or not reactive enough, thereby needing to beregenerated through reaction with one or two hydride sources. However, when the Lewis acid comprises a transition metal, the second halogen reaction is typically less favored, with singlehalide regeneration usually occurring. Although this reaction scheme may sometimes be described herein in terms of what seems like a single hydrodehalogenation, it is possible and sometimes even likely that more than one hydrodehalogenation reaction can occur in series, such that products may therefore contain more than one (sometimes several) less halogen atoms than their corresponding reactant.

[0035] As such, the instant disclosure describes halophosphorane intermediate products, one or more of which may be comprised by the following formula (VP):wherein one of Ri, R2, and R3 is PLsHal, PHL2Hal, or PL2Hah and the other two of Ri, R2, and R3 are each independently H, F, Cl, CH3, or CF3 (in particular, independently H, F, Cl, or CF3; independently H, F, or Cl; or independently H or F); each R4 is independently H, F, or Cl (in particular, independently H or F); Y is O or S (in particular, O); R5 is (CF2)mCF3, with m being 0, 1, or 2 (in particular, with m being 0 or 1); n is 0 or 1 or 2 (in particular, n is 0 or 1); each Hal is independently F or Cl (in particular, each F); and each L is independently a C2-C18 (in particular, a C3-C12, a C3-C6, or the same C3-C4) alkyl group, optionally including a heteroatom selected from oxygen or sulfur, or two or more L’s are connected together to form a C4-C30 (c. ., C4-C26, C5-C24, or C6-C20) phosphorus-containing (hetero)cyclic moiety.

[0036] In some embodiments, because such halophosphorane intermediates / products are made according to the hydrodehalogenation processes described herein, when the optional Lewis acid component is not present in the hydrodehalogenation process (exposing and / or selective reaction steps), the halophosphorane intermediates / products may additionally comprise substantially no transition metals, or substantially no metals from Groups 4 and 6-12 of the Periodic Table of Elements. In hydrodehalogenation processes described herein, whether the optional Lewis acid component is present or not, and in particular when it is present, such halophosphorane intermediates / products may comprise substantially no transition metals from Groups 6-7, 9, andselected from the group consisting of Ag, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof.

[0037] In addition, the instant disclosure further describes “raw” (as-synthesized) compositions containing halophosphorane intermediates / products (made by reaction of the trihydrocarbyl phosphine and the halogen-containing reactant, and such as containing from 6 to 38 carbons, 4 to 26 of which carbons being non-halogenated and pendant from the phosphorous atom, with at least one of the remaining 2 to 12 carbons comprising at least one pendant fluorine atom), typically also comprising the metalloid hydride source and / or the halogen-substituted metalloid compound (reacted hydride source), optionally but typically some unreacted halogen-containing reactant (such as having 2-12 carbon atoms, at least two halogen atoms of which at least one being a fluorine atom, at least one carbon-carbon double bond and / or no hydrogen atoms, and optionally an oxygen or sulfur atom as an ether or thioether, respectively), optionally a metal- or metalloidcontaining Lewis acid whose metal comprises, consists essentially of, or is boron or a transition metal from one or more of Groups 4, 5, 8, and 10 of the Periodic Table of Elements, and optionally a solvent. Except for the halogen-substituted metalloid compound (reacted hydride source), each of these components have descriptions and non-limiting examples provided elsewhere herein and need not be repeated here. Non-limiting examples of the halogen-substituted metalloid compound (reacted hydride source) can include, but are not limited to, a tri(Cl-C6 alkyl)fluorosilane (e.g., tri ethylfluorosilane, triisopropylfluorosilane, or a combination thereof), a mono-fl uoro-tetra(C 1 -C6 alkyl)di siloxane (e.g., l-fluoro-l,l,3,3-tetramethyldisiloxane), a difluoro-tetra(Cl-C6 alkyl)disiloxane (e.g., l,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 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. As noted above, if the hydride source is a metalloid hydride source, the non-limiting examples can therefore include all but a mono-, di-, tri-, or tetra-fluoro-substituted lithium aluminum hydride. Such “raw” compositions may optionally also contain little to no less halogenated (unsaturated) product, as these “raw” compositions can most likely describe the situation during or immediately after the exposing step and / or before, at the beginning of, or during the selective reaction step (but typically before reaction completion to attain significant amounts of hydrodehalogenated products). Whena solvent or mixture of solvents is present in the selective hydrodehalogenation reaction, said “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 can be organic, thus rendering the mixture organic as well).

[0038] Additionally or alternatively, the instant disclosure further describes “raw” (as-synthesized) compositions containing a less halogenated (non-perhalogenated, typically also unsaturated) product (made by reaction of the trihydrocarbyl phosphine and the halogencontaining reactant, such as containing at least one fluorine atom and optionally an oxygen or sulfur atom as an ether or thioether, respectively), the trihydrocarbyl phosphine and / or a hydrocarbyl halophosphine (reacted / halo- substituted version of the phosphine ligand), the (metalloid) hydride source and / or a halogen-substituted hydride compound (reacted version of the hydride source), optionally a (metal- / metalloid- containing) Lewis acid (which metal comprises, consists essentially of, or is a transition metal from one or more of Groups 4, 5, 8, and 10 of the Periodic Table of Elements and which metalloid comprises, consists essentially of, or is boron), and optionally a solvent. Each of these components have descriptions and non-limiting examples provided elsewhere herein and thus need not be repeated here. 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 can be organic, thus rendering the mixture organic as well).

[0039] As mentioned above, for any of the “raw” compositions resulting from reactions described herein, in particular, whether the (metaL / metalloid- containing) Lewis acid is present or not, the selective hydrodehalogenation reaction (both exposing and selective reaction steps) and / or the composition before, during, and / or after said reaction(s) can be characterized as including: less than 500 wppm of metals from Groups 6-7, 9, and 11-12 of the Periodic Table of Elements; less than 200 wppm of metals from Groups 6-7, 9, and 11-12 of the Periodic Table of Elements that do not originate as impurities from the optional organic solvent; or both. Again in particular, when the metal-containing Lewis acid is not present, in particular, the selective hydrodehalogenation reaction (both exposing and selective reaction steps) and / or the composition before, during, and / or after said reaction(s) can be characterized as including: less than 500 wppm (e.g., less than 300 wppm) of metals; less than 200 wppm (c.g., less than 100 wppm) of metals that do not originate as impurities from the optional organic solvent; or both. Further in particular, even when themetalloid-containing Lewis acid is present, in particular, the selective hydrodehalogenation reaction (both exposing and selective reaction steps) and / or the composition before, during, and / or after said reaction(s) can be characterized as including: less than 500 wppm (e. , less than 300 wppm) of metals; less than 200 wppm (e.g., less than 100 wppm) of metals that do not originate as impurities from the optional organic solvent; or both.Additional Embodiments

[0040] Additionally or alternatively, the present disclosure can include one or more of the following embodiments.

[0041] Embodiment 1. A process for selectively hydrodehalogenating a halogen-containing unsaturated reactant to form a less-halogenated unsaturated product comprising: exposing the halogen-containing unsaturated reactant to a trihydrocarbyl phosphine, a metalloid hydride source, and optionally a metal- or metalloid- containing Lewis acid compound to form a halophosphorane intermediate product; and selectively reacting the halophosphorane intermediate product, specifically in the substantial absence of catalysts, hydride sources, and / or ligand complexes comprising a metal selected from the group consisting of Ag, Al, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof, to form the less-halogenated unsaturated product, wherein the selective hydrodehalogenation process results in the less-halogenated unsaturated product having a selectivity of at least 50% for one isomeric species, relative to all products, such as at least 60%, at least 70%, at least 80%, at least 85%, at least 90%, or at least 95%.

[0042] Embodiment 2. The process of embodiment 1, wherein the reactant comprises from 2 to 12 carbon atoms, from 2 to 8 carbon atoms, from 2 to 6 carbon atoms, from 2 to 4 carbon atoms, or from 3 to 6 carbon atoms.

[0043] Embodiment 3. The process of embodiment 1 or embodiment 2, wherein the trihydrocarbyl phosphine comprises, consists essentially of, or is a tri(C2-C18 alkyl) phosphine such as a tri(C3-C12 alkyl) phosphine, l,2-bis(dicyclohexylphosphino)ethane, 1,2-bi s (di cy clopentylphosphino)ethane, 1 ,2-bi s (di i sobutylphosphino)ethane, bi s(2-dicyclohexylphosphinophenyl)ether (DCEphos), an n,n’-bis(diarylphosphino)alkane, an n,n’,n”-tris(diarylphosphino)alkane such as l,2-bis(diphenylphosphino)ethane (Diphos), 1,1’-bis(diphenylphosphino)ferrocene, 1,1,1 -tri s(diphenylphosphinomethyl)ethane (Tripod), bis[2-(diphenylphosphino)ethyl]phenylphosphine (TriPhos), 9-isobutyL9-phosphabicyclo[3.3.1]nonane; 9-isobutyl-9-phosphabicyclo[4.2.1]nonane; 9-n-butyl-9-phosphabicyclo[3.3.1 ]nonane; 9-n-butyl-9-phosphabicyclo[4.2.1 ]nonane; 1 ,2-bis(diisobutylphosphino)ethane; l,3-bis(diisobutylphosphino)propane; 2-n-butyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-n-hexyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-n-decyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-cyclohexylmethyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-benzyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; and 2-(3-hydroxyl-l-propyl)-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane, or a mixture thereof.

[0044] Embodiment 4. The process of any of embodiments 1-3, wherein the metalloid hydride source is present and comprises, consists essentially or, or is a tri(Cl-C6 alkyl)silane, a tetra(Cl-C6 alkyl)disiloxane, a di-(Cl-C6 alkyl) phenylsilane, a (C1-C6 alkyl)diphenyl siloxane, a polysilane, or a mixture thereof.

[0045] Embodiment 5. The process of any of embodiments 1-4, wherein the metal -containing Lewis acid compound comprises, consists essentially of, or is a di-, tri-, or tetra- (C1-C6 alkyl) substituted transition metal from one or more of Groups 4, 5, 8, and 10 of the Periodic Table of Elements, or wherein the metalloid-containing Lewis acid compound comprises boron.

[0046] Embodiment 6. The process of any of embodiments 1-5, wherein the selective reaction and / or exposing steps are performed in the substantial absence of compounds comprising metals from Groups 6-7, 9, and 11-13 of the Periodic Table of Elements.

[0047] Embodiment 7. The process of any of embodiments 1-6, wherein the selective reaction and / or the exposing steps are performed in the presence of a solvent comprising benzene, toluene, a xylene (e.g, m-, p-, o-, or a mixture thereof), mesitylene, chlorobenzene, dichlorobenzene (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, or a mixture thereof.

[0048] Embodiment 8. The process of any of embodiments 1-7, wherein: (1) the exposure is performed at a temperature from 0°C to 100°C, for example from 10°C to 70°C; (2) the selective reaction is performed at a temperature from 20°C to 130°C, for example from 40°C to 110°C or from 50°C to 100°C; or (3) both (1) and (2).

[0049] Embodiment 9. The process of any of embodiments 1-8, further comprising a step of isolating and / or purifying the selective isomeric species, relative to all other products.

[0050] Embodiment 10. The process of any of embodiments 1-9, wherein the less-halogenated unsaturated product comprises trifluoroethylene, chlorodifluoroethylene, di fluoroethylene, hexafluoropropylene, pentafluoropropene, tetrafluoropropene, chloro-trifluoropropene, trifluoropropene, difluoropropene, vinyl fluoride, 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, 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, perfluoro(propenyl methyl ether), trifluoromethyl tetrafluoropropenyl ether, or a mixture thereof.

[0051] Embodiment 12. A halophosphorane according to formula (VP) and / or such as made during or as a result of the selective hydrodehalogenation process according to any one of embodiments 1-11:wherein one of Ri, R2, and R3 is PLsHal, PHL2Hal, or PL2Hah and the other two of Ri, R2, and R3 are each independently H, F, Cl, CH3, or CF3; each R4 is independently H, F, or Cl; Y is O or S; R5 is (CF2)mCF3, with m being 0, 1, or 2; n is 0 or 1 or 2; each Hal is independently F or Cl; and each L is independently a C2-C18 alkyl group optionally including a heteroatom selectedfrom oxygen or sulfur, or two or more L’s are connected together to form a C4-C30 (hetero)cyclic moiety.

[0052] Embodiment 13. The halophosphorane of embodiment 12, wherein one of Ri, R2, and R3 is PLsHal, PHL^Hal, or PL^Hah, and the other two of Ri, R2, and R3 are each independently H, F, Cl, or CF3; each R4 is independently H or F; Y is O or S; R5 is (CF2)mCF3, with m being 0 or 1; n is 0 or 1; each Hal is F; and each Lis independently a C3-C12 alkyl group optionally including a heteroatom selected from oxygen or sulfur, or two or more L’s are connected together to form a C4-C30 (hetero)cyclic moiety.

[0053] Embodiment 14. The halophosphorane of embodiment 13, wherein one of Ri, R2, and R3 is PL3F, PHL2F, or PL2F2, and the other two of Ri, R2, and R3 are each independently H or F; each R4 is independently H or F; Y is O; R5 is CF3; n is 0 or 1; and each L is a C3-12 alkyl group or two or more L’s are connected together to form a C6-C20 (hetero)cyclic moiety.

[0054] Embodiment 15. The halophosphorane of embodiment 14, wherein one of Ri, R2, and R3 is PL3F, PHL2F, or PL2F2, and the other two of Ri, R2, and R3 are both F; each R4 is independently H or F; Y is O; R5 is CF3; n is 0 or 1; and each L is an isobutyl, an n-propyl, or an n-butyl group.

[0055] Embodiment 16. A composition (such as made during or as a result of the selective hydrodehalogenation process according to any one of embodiments 1-11) comprising: a halophosphorane compound made by reaction of a trihydrocarbyl phosphine and a halogencontaining reactant, the halophosphorane compound comprising from 6 to 38 carbons, 4 to 26 of which carbons being non-halogenated and pendant from the phosphorous atom, at least one of the remaining 2 to 12 carbons comprising at least one pendant fluorine atom; an unreacted halogen-containing reactant comprising: 2 to 12 carbon atoms; at least two halogen atoms, at least one of which is a fluorine atom; (a) at least one carbon-carbon double-bond, (b) no hydrogen atoms, or (c) both (a) and (b); and optionally an oxygen or sulfur atom as an ether or thioether, respectively; a metalloid hydride source and / or a halogen-substituted metalloid compound; optionally a Lewis acid comprising a metal that comprises, consists essentially of, or is a transition metal from one or more of Groups 4, 5, 8, and 10 of the Periodic Table of Elements; optionally an organic solvent; and (i) less than 500 wppm of metals from Groups 6-7, 9, and 11-12 of the Periodic Table of Elements, (ii) less than 200 wppm of metals from Groups 6-7, 9, and 11-12 of the Periodic Table of Elements that do not originate as impurities from the optional organic solvent, or (iii) both (i) and (ii).

[0056] Embodiment 17. A composition (such as made during or as a result of the selective hydrodehalogenation process according to any one of embodiments 1-11) comprising: a (C2-C12) non-perhalogenated unsaturated product made by reaction of a trihydrocarbyl phosphine and a halogen-containing reactant, the (C2-C12) non-perhalogenated unsaturated product comprising at least one fluorine atom and optionally an oxygen or sulfur atom as an ether or thioether, respectively; a trihydrocarbyl phosphine and / or a hydrocarbyl halophosphine; a metalloid hydride source and / or a halogen-substituted metalloid compound; optionally an organic solvent; and (i) less than 500 wppm of metals from Groups 6-7, 9, and 11-12 of the Periodic Table of Elements, (ii) less than 200 wppm of metals from Groups 6-7, 9, and 11-12 of the Periodic Table of Elements that do not originate as impurities from the optional organic solvent, or (iii) both (i) and (ii).

[0057] Embodiment 18. The composition of embodiment 17, wherein the (C2-C12) non-perhalogenated unsaturated product comprises trifluoroethylene, chlorodifluoroethylene, difluoroethylene, hexafluoropropylene, pentafluoropropene, tetrafluoropropene, chlorotrifluoropropene, trifluoropropene, difluoropropene, vinyl fluoride, difluoro-(trifluoromethoxy)ethene, fluoro-(trifluoromethoxy)ethene, trifluoromethoxyethene, difluoromethoxyethene, fluoromethoxyethene, pentafluoro-l,3-butadiene, tetrafluoro- 1,3-butadiene, trifluoro- 1,3 -butadiene, difluoro-l,3-butadiene, pentafluorocyclobutene, tetrafluorocyclobutene, trifluorocyclobutene, difluorocyclobutene, fluorocyclobutene, heptafluorobutene, hexafluorobutene, pentafluorobutene, tetrafluorobutene, trifluorobutene, di fluorobutene, fluorobutene, heptafluorocyclopentene, hexafluorocyclopentene, pentafluorocyclopentene, tetrafluorocyclopentene, trifluorocyclopentene, difluorocyclopentene, fluorocyclopentene, nonafluoropentene, octafluoropentene, heptafluoropentene, hexafluoropentene, pentafluoropentene, tetrafluoropentene, trifluoropentene, difluoropentene, hexafluorodihydrothiophene, pentafluorodihydrothiophene, tetrafluorodihydrothiophene, trifluorodihydrothiophene, difluorodihydrothiophene, perfluoro(propenyl methyl ether), trifluoromethyl tetrafluoropropenyl ether, or a mixture thereof.

[0058] Embodiment 19. The composition of embodiment 17 or embodiment 18, wherein the trihydrocarbyl phosphine, when present, comprises, consists essentially of, or is a tri(C2-C18alkyl) phosphine such as atri(C3-C12 alkyl) phosphine, l,2-bis(dicyclohexylphosphino)ethane, l,2-bis(dicyclopentylphosphino)ethane, l,2-bis(diisobutylphosphino)ethane, bis(2-dicyclohexylphosphinophenyl)ether (DCEphos), an n,n’-bis(diarylphosphino)alkane, an n,n’,n”-tris(diarylphosphino)alkane such as l,2-bis(diphenylphosphino)ethane (Diphos), 1,1’-bis(diphenylphosphino)ferrocene, l,l,l-tris(diphenylphosphinomethyl)ethane (Tripod), bis[2-(diphenylphosphino)ethyl]phenylphosphine (TriPhos), 9-isobutyl-9-phosphabicyclo[3.3. l]nonane; 9-isobutyl-9-phosphabicyclo[4.2.1]nonane; 9-n-butyl-9-phosphabicyclo[3.3.1]nonane; 9-n-butyl-9-phosphabicyclo[4.2.1]nonane; 1,2-bis(diisobutylphosphino)ethane; l,3-bis(diisobutylphosphino)propane; 2-n-butyl-4,8-dimethyl-2-phosphabicyclo[3.3.1 ]nonane; 2-n-hexyl-4, 8-dimethyl-2-phosphabicyclo[3.3.1 ]nonane; 2-n-decyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-cyclohexylmethyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-benzyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; and 2-(3-hydroxyl-l-propyl)-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane, or a mixture thereof (e.g, comprises, consists essentially of, or is a tri(C3-C6 alkyl) phosphine, such as a tri(C3-C4 alkyl) phosphine).

[0059] Embodiment 20. The composition of any one of embodiments 16-19, wherein the metalloid hydride source, when present, comprises atri(Cl-C6 alkyl)fluorosilane, a mono-fluoro-tetra(Cl-C6 alkyl)disiloxane, a difluoro-tetra(Cl-C6 alkyl)disiloxane, a (C1-C6 alkyl)diarylfluorosilane, a di-(Cl-C6 alkyl)arylfluorosilane, or a mixture thereof, and wherein the halogen-substituted metalloid compound, when present, comprises a tri(Cl-C6 alkyl)fluorosilane, a mono-fluoro-tetra(Cl-C6 alkyl)di siloxane, a difluoro-tetra(Cl-C6 alkyl)disiloxane, a (C1-C6 alkyl)diarylfluorosilane, a di-(Cl-C6 alkyl )arylfluorosilane, or a mixture thereof.

[0060] Embodiment 21. The composition of any of embodiments 16-20, wherein the solvent is present and comprises benzene, toluene, a xylene (e.g., m-, p-, o-, or a mixture thereof), mesitylene, chlorobenzene, dichlorobenzene (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-di oxane, formaldehyde,acetaldehyde, acetonitrile, petroleum distillate, petroleum spirits, kerosene, hexane, heptane, octane, cyclohexane, cycloheptane, cyclooctane, norbomane, adamantane, or a mixture thereof.

[0061] Embodiment 22. The composition of any of embodiments 16-21, (a) comprising (i) less than 300 wppm of metals selected from the group consisting of Ag, Al, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof, (ii) less than 100 wppm of metals selected from the group consisting of Ag, Al, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof that do not originate as impurities from the optional organic solvent, or (iii) both (i) and (ii); and / or (b) comprising (i) less than 500 wppm of metals, (ii) less than 200 wppm of metals that do not originate as impurities from the optional organic solvent, or (iii) both (i) and (ii).

[0062] 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 “consisting essentially of’, respectively, the latter of which should be understood to be given the meaning provided by United States case law as of the filing and / or priority date(s) hereof, as applicable. EXAMPLESExperiments were conducted under dry nitrogen using an MBraun glovebox. Glassware was dried in an oven set at 120°C for 2 h before use. Benzene (>99.5%, TCI America, Montgomeryville, PA) and benzene-de (99.5%, Cambridge Isotope Laboratories, Tewksbury, MA) were deoxygenated and dried over 3A molecular sieves activated at >200°C in a vacuum oven before use. Titanium isopropoxide (97%, Sigma-Aldrich, Oakville, ON), benzotrifluoride (anhydrous >99%, Sigma-Aldrich, Oakville, ON), 1,1,3,3-tetramethyldisiloxane (97%, Sigma-Aldrich, Oakville, ON), and all other ligand additives, hydride were used as received. All alkylphosphines were manufactured by Cytec Canada (now Solvay, Niagara Falls, ON) and distributed by Strem (Newburyport, MA) under the CYTOP® tradename. Perfluoro(methyl vinyl ether) (PMVE, 99%), and hexafluoropropylene (HFP, 98.5%) were used as received from Synquest Laboratories (Alachua, FL). NMR spectra were recorded on a 500 MHz Bruker Avance III instrument at room temperature (17-23°C).19F spectra were referenced to an internal standard of PhCFa (8 ~ - 63.5 ppm) and31P spectra were referenced to an external standard of H3PO4 (85% aqueous solution, 8 = 0 ppm). Product selectivity values calculated from19F NMR spectra excluded traces of non-volatile halophosphorane intermediate products, which were minor by-products in each case, and thus represent “normalized” product selectivities. With ether-containing reactants (PMVE), spectra were additionally normalized to exclude de-etherified by-products (such as E- / Z- 1225ye, which are yielded from a detrifluoromethoxylation instead of a defluorination reaction).Without being bound by theory, the following set of reaction mechanisms may provide insight into phosphine-mediated selective hydrodehalogenation reaction(s), with and without the Lewis acid component, such as described in the present disclosure. Although the reaction mechanisms are shown as relating to hexafluoropropene (HFP) or perfluoro(methyl vinyl ether) (PMVE) (perhalogenated) reactants, the ordinary skilled artisan should be able to adjust the teachings to other reactants (such as chlorotrifluoroethylene / CTFE et al.). In addition, while the reaction mechanisms below only show multiple hydrodehalogenation steps with respect to HFP and not strictly to PMVE, it should be understood that PMVE reactant (and indeed other reactants such as CTFE, or even those with some halogen atoms but not perhalogenated) can undergo multiple hydrodehalogenation steps, whether individually or simultaneously according to the processes of the present disclosure, in order to attain various halophosphorane (intermediate) products / by-products and / or multiply hydrodehalogenated (less halogenated) products / compositions according to the present disclosure.Examples 1-6, Phosphine Hydrodefluorination of hexafluoropropylene (HFP; CaFe)Example 1 was performed on a -0.123 mmol scale. Tn the nitrogen-filled glovebox, an ~8” NMR tube was charged with tri(n-propyl)phosphine (P(nPr)3; -0.123 mmol; -1.0 equivalents), benzotrifluoride (-50 zzL of -0.246M solution in benzene), 1,1,3,3-tetramethyldisilane (TMDS) (-2 equivalents, -0.246 mmol, -43 / zL), and diluted with -600 / zL with benzene. The NMR tube was sealed with a fresh (never punctured) rubber septum cap, tightly wrapped with parafilm, and charged with -3 mL of hexafluoropropylene (-0.123 mmol) bubbled directly into the solution by injection through a ~23-gauge needle. The NMR tube was then immersed to the solvent level in an aluminum bead bath and left to ripen overnight (-18 hours) at ~70°C, after which it was cooled to room temperature (~17-23°C) and analyzed by19F and31P NMR. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -0% Z-1225ye, -23% E-1225ye, and -77% 1234yf. See reaction scheme below.F PR3(0.5—1 equiv.) F FF7(FC, 18 h 1225ye 1234yfExample 2 was identical to Example 1, except that the P(nPr)s concentration was halved to -0.5 equivalents. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -2% Z-1225ye, -82% E-1225ye, and -16% 1234yf Example 3 was identical to Example 1, except that the P(nPr)s phosphine was replaced with tri(n-butyl)phosphine (P(nBu)s) at the same concentration of -1.0 equivalents. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -3% Z-1225ye, -2% E-1225ye, and -95% 1234yf.Example 4 was identical to Example 3, except that the P(nBu)s concentration was halved to -0.5 equivalents. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -3% Z-1225ye, -6% E-1225ye, and -91% 1234yf.Example 5 was identical to Example 1, except that the P(nPr)3 phosphine was replaced with tri(isobutyl)phosphine (P(iBu)s) at the same concentration of -1.0 equivalents. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -0% Z-1225ye, -94% E-1225ye, and -6% 1234yf.Example 6 was identical to Example 5, except that the P(iBu)s concentration was halved to -0.5 equivalents. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -0% Z-1225ye, -97% E-1225ye, and -3% 1234yfExamples 7-12, Phosphine Hydrodefluorination of hexafluoropropylene (HFP; C3F6) in Presence of TitaniumExample 7 was identical to Example 2, except that titanium (IV) tetraisopropoxide (Ti(OiPr)4) was added as a Lewis acid at a concentration of ~0.5 equivalents. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -0% Z-1225ye, -68% E-1225ye, and -32% 1234yf.Example 8 was identical to Example 7, except that the reaction time was increased to -40 hours. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -42% Z-1225ye, -21% E-1225ye, and -37% 1234yf.Example 9 was identical to Example 8, except that the P(nPr)3 phosphine was replaced with tri(n-butyl)phosphine (P(nBu)s) at the same concentration of -0.5 equivalents. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -14% Z-1225ye, -74% E-1225ye, and -12% 1234yf.Example 10 was identical to Example 6, except that titanium (IV) tetraisopropoxide (Ti(OiPr)4) was added as a Lewis acid at a concentration of -0.5 equivalents. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -17% Z-1225ye, -82% E-1225ye, and -6% 1234yf.Example 11 was identical to Example 10, except that the reaction time was increased to -40 hours. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -16% Z-1225ye, -67% E-1225ye, and -17% 1234yf.Comparative Example 12 was identical to Example 7, except that the P(nPr)3 phosphine component was eliminated. In this case, normalized conversion was observed to be -44%, with products being -19% Z-1225ye, -25% E-1225ye, and -0% 1234yf, with other products remaining unidentified.Examples 13-19, Phosphine Hydrodefluorination of Perfluoro(Methyl Vinyl Ether) (PMVE;C3F6O)Example 13 was performed on a -0.123 mmol scale. In the nitrogen-filled glovebox, an -8” NMR tube was charged with tri(n-propyl)phosphine (P(nPr)3; -0.123 mmol; -1.0 equivalents), benzotrifluoride (-50 / / L of -0.246M solution in benzene), 1, 1,3,3-tetramethyldisilane (TMDS) (-2 equivalents, -0.246 mmol, -43 «L), and diluted with -600 «L with benzene. The NMR tube was sealed with a fresh (never punctured) rubber septum cap, andtightly wrapped with parafilm, and charged with -3 mL of perfluoro(vinyl methyl ether) (PVME; -0.123 mmol) bubbled directly into the solution by injection through a ~23-gauge needle. The NMR tube was then immersed to the solvent level in an aluminum bead bath and left to ripen overnight (-18 hours) at ~50°C, after which it was cooled to room temperature (~17-23°C) and analyzed by19F and31P NMR. In this case, normalized conversion was observed to be -80%, with products being -15% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye) and -65% E-1,2-difluoro-l-(trifluoromethoxy)ethene (E-E1225ye). See the reaction scheme below.Example 14 was identical to Example 13, except that the P(nPr)3 concentration was halved to -0.5 equivalents. In this case, normalized conversion was observed to be -22%, with products being -5% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye) and -17% E-l,2-difluoro-l-(trifluorom ethoxy )ethene (E-E1225ye).Example 15 was identical to Example 13, except that the P(nPr)3 phosphine was replaced with tri(n-butyl)phosphine (P(nBu)s) at the same concentration of -1.0 equivalents. In this case, normalized conversion was observed to be -94%, with products being -22% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye) and -72% E-l,2-difluoro-l-(trifluoromethoxy)ethene (E-E1225ye).Example 16 was identical to Example 15, except that the P(nBu)s concentration was halved to -0.5 equivalents. In this case, normalized conversion was observed to be -32%, with products being -6% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye) and -26% E-l,2-difluoro-l-(trifluorom ethoxy )ethene (E-E 1225y e).Example 17 was identical to Example 13, except that the P(nPr)s phosphine was replaced with tri(isobutyl)phosphine (P(iBu)s) at the same concentration of -1.0 equivalents. In this case, normalized conversion was observed to be -50%, with products being -9% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye) and -41% E-l,2-difluoro-l-(trifluorom ethoxy )ethene (E-E1225ye), as well as a significant amount (-22%) of a non-volatile phosphorane intermediate (considered only partial conversion and thus unrepresented in the normalized conversion value).Example 18 was identical to Example 17, except that the P(iBu)s concentration was halved to -0.5 equivalents. In this case, normalized conversion was observed to be -31%, with productsbeing -5% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye) and ~26% E-l,2-difluoro-l-(trifluoromethoxy)ethene (E-E1225ye), as well as a significant amount (-38%) of a non-volatile phosphorane intermediate (considered only partial conversion and thus unrepresented in the normalized conversion value).Examples 19-22, Phosphine Hydrodefluorination of Perfluoro(Methyl Vinyl Ether) (PMVE; C3F6O) in Presence of TitaniumExample 19 was identical to Example 14, except that titanium (IV) tetraisopropoxide (Ti(OiPr)4) was added as a Lewis acid at a concentration of -0.5 equivalents. In this case, normalized conversion was observed to be -67%, with products being -23% Z-l,2-difluoro-l-(trifluoromethoxy)ethene and -34% E-l,2-difluoro-l-(trifluoromethoxy)ethene.Example 20 was identical to Example 19, except that the P(nPr)s phosphine was replaced with tri(n-butyl)phosphine (P(nBu)s) at the same concentration of -0.5 equivalents. In this case, normalized conversion was observed to be -54%, with products being -18% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye) and -36% E-l,2-difluoro-l-(trifluorom ethoxy )ethene (E-E1225ye).Example 21 was identical to Example 18, except that titanium (IV) tetraisopropoxide (Ti(OiPr)4) was added as a Lewis acid at a concentration of -0.5 equivalents. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -15% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye) and -35% E-l,2-difluoro-l-(trifluorom ethoxy )ethene (E-E1225ye).Comparative Example 22 was identical to Example 19, except that the P(nPr)3 phosphine component was eliminated. In this case, normalized conversion was observed to be -12%, with products being -8% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye) and -4% E-1,2-difluoro-l-(trifluoromethoxy)ethene (E-E1225ye).Examples 23-44, Phosphine Hydrodefluorination of hexafluoropropylene (HFP; C3F6) in Presence of TitaniumExample 23 was identical to Example 9, except that: the P(iBu)3 and Ti(OiPr)4 concentrations were both reduced slightly to -0.4 equivalents each; the TMDS concentration was approximately doubled to -4 equivalents; and the reaction temperature was decreased to ~50°C. In this case, normalized conversion was observed to be -86%, with products being -12% Z-1225ye, -74% E-1225ye, -0% 1234yf, and -0% 1234ze.Examples 24-33 were identical to Example 23, except that the P(iBu)s phosphine component was replaced by each of a variety of other phosphines, each at the same concentration of ~0.4 equivalents: 9-isobutyl-9-phosphabicyclo[3.3.1]nonane and / or 9-isobutyl-9-phosphabicyclo[4.2.1]nonane (such as in a weight ratio of -3:1; iBu-Phob; Example 24); 9-n-butyl-9-phosphabicyclo[3.3.1]nonane and / or 9-n-butyl-9-phosphabicyclo[4.2.1]nonane (such as in a weight ratio of -3:1; nBu-Phob; Example 25); l,2-bis(diisobutylphosphino)ethane (Example 26); l,3-bis(diisobutylphosphino)propane (Example 27); 2-n-butyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane (Lim-4; Example 28); 2-n-hexyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane (Lim-6; Example 29); 2-n-decyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane (Lim-10; Example 30); 2-cyclohexylmethyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane (Lim-CyMe; Example 31); 2-benzyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane (Lim-Bn; Example 32); and 2-(3-hydroxyl-l-propyl)-4,8-dimethyl- 2-phosphabicyclo[3.3.1]nonane (Lim-HP; Example 33). In these cases, normalized conversion was observed as follows, with the following products: Example 24 — 87% conversion to -21% Z-1225ye, -66% E-1225ye, -0% 1234yf, and -0% 1234ze; Example 25 — 92%> conversion to -23% Z-1225ye, -69% E-1225ye, -0% 1234yf, and -0% 1234ze; Example 26 — 77% conversion to -9% Z-1225ye, -68% E-1225ye, -0% 1234yf, and -0% 1234ze; Example 27 - -74% conversion to -12% Z-1225ye, -62% E-1225ye, -0% 1234yf, and -0% (trace) 1234ze; Example 28 - -100% (essentially complete) conversion to -27% Z-1225ye, -69% E-1225ye, -4% 1234yf, and -0% 1234ze; Example 29 — 100% (essentially complete) conversion to -24% Z-1225ye, -74% E-1225ye, -2% 1234yf, and -0% 1234ze; Example 30 - -100% (essentially complete) conversion to -29% Z-1225ye, -71% E-1225ye, -0% 1234yf, and -0% 1234ze; Example 31 --100% (essentially complete) conversion to -32% Z-1225ye, -65% E-1225ye, -3% 1234yf, and -0% 1234ze; Example 32 — 70% conversion to -15% Z-1225ye, -55% E-1225ye, -0% 1234yf, and -0% 1234ze; and Example 33 — 98% (essentially complete) conversion to -17% Z-1225ye, -62% E-1225ye, -19% 1234yf, and -0% (trace) 1234ze.Example 34 was identical to Example 33, except that the Lim-HP and Ti(OiPr)4 concentrations were both increased to -0.6 equivalents each. In this case, normalized conversion was observed to be -99% (essentially complete), with products being -16% Z-1225ye, -61% E-1225ye, -22% 1234yf, and -0% (trace) 1234ze.Example 35 was identical to Example 34, except that the reaction temperature was reduced to room temperature (~17-23°C). In this case, normalized conversion was observed to be -85%, with products being -4% Z-1225ye, -81% E-1225ye, -0% 1234yf, and -0% (trace) 1234ze.Example 36 was identical to Example 33, except that the Lim-HP concentration was increased to -0.8 equivalents. In this case, normalized conversion was observed to be -98% (essentially complete), with products being -4% Z-1225ye, -51% E-1225ye, -43% 1234yf, and -0% (trace) 1234ze.Example 37 was identical to Example 33, except that the Ti(OiPr)4 concentration was increased to -0.8 equivalents. In this case, normalized conversion was observed to be -99% (essentially complete), with products being -15% Z-1225ye, -50% E-1225ye, -34% 1234yf, and -0% (trace) 1234ze.Example 38 was identical to Example 36, except that the Ti(OiPr)4 concentration was increased to -0.8 equivalents. In this case, normalized conversion was observed to be -99% (essentially complete), with products being -3% Z-1225ye, -26% E-1225ye, -70% 1234yf, and -0% (trace) 1234ze.Example 39 was identical to Example 38, except that the Lim-HP and Ti(OiPr)4 concentrations were both increased to -1.0 equivalents each. In this case, normalized conversion was observed to be -86%, with products being -2% Z-1225ye, -6% E-1225ye, -78% 1234yf, and -0% (trace) 1234ze.Example 40 was identical to Example 39, except that the Lim-HP and Ti(OiPr)4 concentrations were both increased to -1.1 equivalents (-0.14 mmol) each. In this case, normalized conversion was observed to be -99% (essentially complete), with products being -1% Z-1225ye, -7% E-1225ye, -91% 1234yf, and -0% (trace) 1234ze.Example 41 was identical to Example 40, except that the Lim-HP and Ti(OiPr)4 concentrations were both increased to -1.3 equivalents each. In this case, normalized conversion was observed to be -99% (essentially complete), with products being -1% Z-1225ye, -3% E-1225ye, -96% 1234yf, and -0% (trace) 1234ze.Example 42 was identical to Example 41, except that the Lim-HP concentration was reduced back to -0.4 equivalents. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -0% (trace) Z-1225ye, -0% (trace) E-1225ye, -78% 1234yf, -0% (trace) 1234ze, and the remainder 1,1,1,2-tetrafluoropropane (245eb).Example 43 was identical to example 41, except that the Ti(OiPr)4 concentration was reduced back to ~0.4 equivalents. In this case, normalized conversion was observed to be -96%, with products being -0% (trace) Z-1225ye, -38% E-1225ye, -58% 1234yf, and -0% (trace) 1234ze.Example 44 was identical to Example 23, except that the Ti(OiPr)4 Lewis acid was replaced by triphenylborane (BPha) at the same concentration of -0.4 equivalents (-0.05 mmol). In this case, normalized conversion was observed to be -61%, with products being -7% Z-1225ye, -54% E-1225ye, and~0% 1234yf.Examples 45-58, Phosphine Hydrodefluorination and / or Hydrodechlorination of Chlorotrifluoroethylene (CTFE; C2F3CI) in Presence of TitaniumIn these Examples 45-58, in addition to other “normalizations” mentioned herein, the conversion values were further normalized to exclude non-enumerated and unspecified fluoroolefins.Example 45 was performed on a -0.123 mmol scale. In the nitrogen-filled glovebox, an -8” NMR tube was charged with tri(isobutyl)phosphine (P(iBu)a; -0.05 mmol; -0.4 equivalents), 1,1,3,3-tetramethyldisilane (TMDS) (-4 equivalents, -0.5 mmol, -90 «L), titanium (IV) tetraisopropoxide (Ti(OiPr)4; -0.05 mmol, -0.4 equivalents), and diluted with -600 wL with benzene (CeDe). The NMR tube was sealed with a fresh (never punctured) rubber septum cap, and tightly wrapped with parafilm, and charged with -3 mb of chlorotrifluoroethylene (CTFE; -0.123 mmol) bubbled directly into the solution by injection through a ~23-gauge needle. The NMR tube was then immersed to the solvent level in an aluminum bead bath and left to ripen overnight (-18 hours) at ~50°C, after which it was cooled to room temperature (~17-23°C) and analyzed by19F and31P NMR. In this case, normalized conversion was observed to be -26%, with products being ~16%Z-1122a, ~5% E-1122a, ~5% Z-1132, and -0% (trace) 1131 (enantiomers not resolved).Examples 46-55 were identical to Example 45, except that the P(iBu)s phosphine component was replaced by each of a variety of other phosphines, each at the same concentration of -0.4 equivalents: 9-isobutyl-9-phosphabicyclo[3.3.1]nonane and / or 9-isobutyl-9-phosphabicyclo[4.2.1]nonane (such as in a weight ratio of -3:1; iBu-Phob; Example 46); 9-n-butyl-9-phosphabicyclo[3.3.1]nonane and / or 9-n-butyl-9-phosphabicyclo[4.2.1]nonane (such as in a weight ratio of -3:1; nBu-Phob; Example 47); l,2-bis(diisobutylphosphino)ethane (dibpe; Example 48); l,3-bis(diisobutylphosphino)propane (dibpp; Example 49); Lim-4 (Example 50);Lim-6 (Example 51); Lim-10 (Example 52); Lim-CyMe (Example 53); Lim-Bn (Example 54); and Lim-HP (Example 55). In these cases, normalized conversion was observed as follows, with the following products: Example 46 — 31% conversion to -15% Z- 1122a, -5% E- 1122a, -5% Z-1132, and -0% 1131 (enantiomers not resolved); Example 47 — 46% conversion to -29% Z-1122a, -3% E-1122a, -14% Z-1132, and -0% (trace) E-1132; Example 48 - -38% conversion to -20% Z-1122a, -3% E-1122a, -15% Z-1132, and -0% (trace) 1131 (enantiomers not resolved); Example 49 - -32% conversion to -17% Z-1122a, -2% E-1122a, -13% Z-1132, -0% (trace) E-1132, and -0% (trace) 1131 (enantiomers not resolved); Example 50 — 42% conversion to -27% Z- 1122a, -38% E- 1122a, -58% Z-1132, and -0% (trace) 1131 (enantiomers not resolved); Example 51 — 34% conversion to -18% Z-1122a, -5% E-1122a, -11% Z-1132, and -0% (trace) 1131 (enantiomers not resolved); Example 52 — 37% conversion to -20% Z- 1122a, -5% E- 1122a, -12% Z-1132, and -0% (trace) 1131 (enantiomers not resolved); Example 53 — 0% (substantially no) conversion; Example 54 — 29% conversion to -17% Z-1122a, -2% E-1122a, -10% Z-1132, and~0% 1131 (enantiomers not resolved); and Example 55 — 49% conversion to -21% Z- 1122a, -8% E-1122a, -10% Z-1132, and -0% (trace) 1131 (enantiomers not resolved).Example 56 was identical to Example 47, except that the Ti(OiPr)4 concentration was increased to -0.8 equivalents. In this case, normalized conversion was observed to be -42%, with products being -19% Z-1122a, -2% E-1122a, -21% Z-1132, and -0% 1131 (enantiomers not resolved).Example 57 was identical to Example 47, except that the nBu-Phob phosphine concentration was increased to -0.8 equivalents. In this case, normalized conversion was observed to be -51%, with products being -26% Z-1122a, -8% E-1122a, -17% Z-1132, and -0% 1131 (enantiomers not resolved).Example 58 was identical to Example 56, except that the nBu-Phob phosphine concentration was increased to -0.8 equivalents. In this case, normalized conversion was observed to be -70%, with products being -32% Z-1122a, -9% E-1122a, -29% Z-1132, and -0% 1131 (enantiomers not resolved).Examples 59-72, Phosphine Hydrodefluorination of Perfluoro(Methyl Vinyl Ether) (PMVE; C3F6O) in Presence of TitaniumIn these Examples 59-72, in addition to other “normalizations” mentioned herein, the conversion values were further normalized to exclude non-enumerated and unspecified fluoroolefins.Example 59 was performed on a -0.123 mmol scale. In the nitrogen-filled glovebox, an -8” NMR tube was charged with tri(isobutyl)phosphine (P(iBu)s; -0.05 mmol; -0.4 equivalents), 1,1,3,3-tetramethyldisilane (TMDS) (-4 equivalents, -0.5 mmol, -90 z / L), titanium (IV) tetraisopropoxide (Ti(OiPr)4; -0.05 mmol, -0.4 equivalents), and diluted with -600 / / L with benzene (CeDe). The NMR tube was sealed with a fresh (never punctured) rubber septum cap, and tightly wrapped with parafilm, and charged with -3 mL of PMVE (-0.123 mmol) bubbled directly into the solution by injection through a -23 -gauge needle. The NMR tube was then immersed to the solvent level in an aluminum bead bath and left to ripen overnight (-18 hours) at ~50°C, after which it was cooled to room temperature (~17-23°C) and analyzed by19F and31P NMR. In this case, normalized conversion was observed to be -64%, with products being -39% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye), -25% E-l,2-difluoro-l-(trifluoromethoxy)ethene (E-E1225ye), and -0% (trace) 1132 (E- / Z- enantiomers not resolved).Examples 60-69 were identical to Example 59, except that the P(iBu)s phosphine component was replaced by each of a variety of other phosphines, each at the same concentration of -0.4 equivalents: 9-isobutyl-9-phosphabicyclo[3.3.1]nonane and / or 9-isobutyl-9-phosphabicyclo[4.2.1]nonane (iBu-Phob; Example 60); 9-n-butyl-9-phosphabicyclo[3.3.1]nonane and / or 9-n-butyl-9-phosphabicyclo[4.2.1]nonane (nBu-Phob; Example 61); 1,2-bis(diisobutylphosphino)ethane (dibpe; Example 62); l,3-bis(diisobutylphosphino)propane (dibpp; Example 63); Lim-4 (Example 64); Lim-6 (Example 65); Lim-10 (Example 66); Lim-CyMe (Example 67); Lim-Bn (Example 68); and Lim-HP (Example 69). In these cases, normalized conversion was observed as follows, with the following products: Example 60 — 61% conversion to -35% Z-l,2-difluoro-l -(trifluoromethoxy )ethene (Z-E1225ye), -26% E-1,2-difluoro- 1 -(trifluoromethoxy)ethene (E-E1225ye), and -0% 1132 (E- / Z- enantiomers not resolved); Example 61 — 50% conversion to -30% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye), -20% E-l,2-difluoro-l-(trifluoromethoxy)ethene (E-E1225ye), and -0% 1132 (E- / Z-enantiomers not resolved); Example 62 - -70% conversion to -40% Z-l,2-difluoro-l-(trifluorom ethoxy )ethene (Z-E1225ye), -10% E-l,2-difluoro-l-(trifluoromethoxy)ethene (E-E1225ye), and -20% Z-1132; Example 63 - -64% conversion to -40% Z-l,2-difluoro-l-(trifluoromethoxy )ethene (Z-E1225ye), -16% E-l,2-difluoro-l-(trifluoromethoxy)ethene (E-E1225ye), and -8% Z-1132; Example 64 - -72% conversion to -34% Z-l,2-difluoro-l-(trifluorom ethoxy )ethene (Z-E1225ye), -38% E-l,2-difluoro-l-(trifluoromethoxy)ethene (E-E1225ye), and -0% 1132 (E- / Z- enantiomers not resolved); Example 65 — 66% conversion to -28% Z-l,2-difluoro-l-(trifluorom ethoxy )ethene (Z-E1225ye), -38% E-l,2-difluoro-l- (trifluoromethoxy)ethene (E-E1225ye), and -0% 1132 (E- / Z- enantiomers not resolved); Example 66 — 62% conversion to -38% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye), -24% E-1,2-difluoro-l -(trifluoromethoxy )ethene (E-E1225ye), and -0% (trace) 1132 (E- / Z- enantiomers not resolved); Example 67 — 66% conversion to -44% Z-l ,2-difluoro-l -(trifluoromethoxy)ethene (Z-E1225ye), -22% E-l,2-difluoro-l-(trifluorom ethoxy )ethene (E-E1225ye), and -0% (trace) 1132 (E- / Z- enantiomers not resolved); Example 68 — 65% conversion to -40% Z-l,2-difluoro-1 -(trifluoromethoxy)ethene (Z-E1225ye), -25% E- 1 ,2-difluoro- 1 -(trifluoromethoxy)ethene (E-E1225ye), and -0% 1132 (E- / Z- enantiomers not resolved); and Example 69 — 39% conversion to -28% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye), -11% E-l,2-difluoro-l-(trifluoromethoxy)ethene (E-E1225ye), and -0% 1132 (E- / Z- enantiomers not resolved).Example 70 was identical to Example 69, except that the Ti(OiPr)4 concentration was increased to -0.8 equivalents. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -64% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye) and -36% E- 1 ,2-difluoro- 1 -(trifluorom ethoxy )ethene (E-E1225ye).Example 71 was identical to Example 69, except that the Lim-HP phosphine concentration was increased to -0.8 equivalents. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -60% Z-l,2-difluoro-l -(trifluorom ethoxy )ethene (Z-E1225ye) and -40% E-l,2-difluoro-l -(trifluorom ethoxy)ethene (E-E1225ye).Example 72 was identical to Example 71, except that the Lim-HP phosphine concentration was increased to -0.8 equivalents. In this case, normalized conversion was observed to be -100% (essentially complete), with products being -52% Z-l,2-difluoro-l-(trifluoromethoxy)ethene (Z-E1225ye) and -48% E- 1 ,2-difluoro- 1 -(trifluorom ethoxy )ethene (E-E1225ye).

Claims

CLAIMSWhat is claimed is:

1. A process for selectively hydrodehalogenating a halogen-containing unsaturated reactant to form a less-halogenated unsaturated product comprising:exposing the halogen-containing unsaturated reactant to a trihydrocarbyl phosphine, a metalloid hydride source, and optionally a metal- or metalloid- containing Lewis acid compound to form a halophosphorane intermediate product; andselectively reacting the halophosphorane intermediate product, specifically in the substantial absence of catalysts, hydride sources, and / or ligand complexes comprising a metal selected from the group consisting of Ag, Al, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof, to form the less-halogenated unsaturated product,wherein the selective hydrodehalogenation process results in the less-halogenated unsaturated product having a selectivity of at least 50% for one isomeric species, relative to all products.

2. The process of claim 1, wherein the reactant comprises from 2 to 8 carbon atoms, from 2 to 6 carbon atoms, from 2 to 4 carbon atoms, or from 3 to 6 carbon atoms.

3. The process of claim 1 or claim 2, wherein the trihydrocarbyl phosphine comprises, consists essentially of, or is a tri(C2-C18 alkyl) phosphine such as atri(C3-C12 alkyl) phosphine, l,2-bis(dicyclohexylphosphino)ethane, l,2-bis(dicyclopentylphosphino)ethane, 1,2-bis(diisobutylphosphino)ethane, bis(2-dicyclohexylphosphinophenyl)ether (DCEphos), an n,n’-bis(diarylphosphino)alkane, an n,n’,n”-tris(diarylphosphino)alkane such as 1,2-bis(diphenylphosphino)ethane (Diphos), l,l’-bis(diphenylphosphino)ferrocene, 1,1,1-tris(diphenylphosphinomethyl)ethane (Tripod), bis[2-(diphenylphosphino)ethyl]phenylphosphine (TriPhos), 9-isobutyl-9-phosphabicyclo[3.

3. l]nonane; 9-isobutyl-9-phosphabicyclo[4.2.1]nonane; 9-n-butyl-9-phosphabicyclo[3.3.1]nonane; 9-n-butyl-9-phosphabicyclo[4.2.1]nonane; l,2-bis(diisobutylphosphino)ethane; 1,3-bis(diisobutylphosphino)propane; 2-n-butyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-n-hexyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-n-decyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-cyclohexylmethyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-benzyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; and 2-(3-hydroxyl-l-propyl)-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane, or a mixture thereof.

4. The process of any of claims 1-3, wherein the metalloid hydride source is present and comprises, consists essentially or, oris atri(Cl-C6 alkyl)silane, atetra(Cl-C6 alkyl)disiloxane, a di-(Cl-C6 alkyl) phenylsilane, a (C1-C6 alkyl)diphenylsiloxane, a polysilane, or a mixture thereof.

5. The process of any of claims 1-4, wherein the metal-containing Lewis acid compound comprises, consists essentially of, or is a di-, tri-, or tetra- (C1-C6 alkyl) substituted transition metal from one or more of Groups 4, 5, 8, and 10 of the Periodic Table of Elements, or wherein the metalloid-containing Lewis acid compound comprises boron.

6. The process of any of claims 1-5, wherein the selective reaction and / or exposing steps are performed in the substantial absence of compounds comprising metals from Groups 6-7, 9, and 11-13 of the Periodic Table of Elements.

7. The process of any of claims 1-6, wherein the selective reaction and / or the exposing steps are 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, 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, norbomane, adamantane, or a mixture thereof.

8. The process of any of claims 1-7, wherein:(1) the exposure is performed at a temperature from 0°C to 100°C, for example from 10°C to 70°C;(2) the selective reaction is performed at a temperature from 20°C to 130°C, for example from 40°C to 110°C or from 50°C to 100°C; or(3) both (1) and (2).

9. The process of any of claims 1-8, wherein the less-halogenated unsaturated product has a selectivity of at least 60%, at least 70%, at least 80%, at least 85%, at least 90%, or at least 95%.

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

11. The process of any of claims 1-10, wherein the less-halogenated unsaturated product comprises trifluoroethylene, chlorodifluoroethylene, difluoroethylene, hexafluoropropylene, pentafluoropropene, tetrafluoropropene, chloro-trifluoropropene, trifluoropropene, difluoropropene, vinyl fluoride, difluoro-(trifluoromethoxy)ethene, fluoro-(trifluoromethoxy)ethene, trifluoromethoxyethene, difluoromethoxyethene, fluoromethoxyethene, pentafluoro-l,3-butadiene, tetrafluoro- 1,3 -butadiene, trifluoro- 1,3-butadiene, difluoro-l,3-butadiene, pentafluorocyclobutene, tetrafluorocyclobutene, trifluorocyclobutene, difluorocyclobutene, fluorocyclobutene, heptafluorobutene, hexafluorobutene, pentafluorobutene, tetrafluorobutene, trifluorobutene, di fluorobutene, fluorobutene, heptafluorocyclopentene, hexafluorocyclopentene, pentafluorocyclopentene, tetrafluorocyclopentene, trifluorocyclopentene, difluorocyclopentene, fluorocyclopentene, nonafluoropentene, octafluoropentene, heptafluoropentene, hexafluoropentene, pentafluoropentene, tetrafluoropentene, trifluoropentene, difluoropentene, hexafluorodihydrothiophene, pentafluorodihydrothiophene, tetrafluorodihydrothiophene, trifluorodihydrothiophene, difluorodihydrothiophene, perfluoro(propenyl methyl ether), trifluoromethyl tetrafluoropropenyl ether, or a mixture thereof.

12. A halophosphorane according to formula (VP):wherein one of Ri, R2, and R3 is PLsHal, PHL2Hal, or PL2Hah and the other two of Ri, R2, and R3 are each independently H, F, Cl, CH3, or CF3; each R4 is independently H, F, or Cl; Y is O or S; R5 is (CF2)mCF3, with m being 0, 1, or 2; n is 0 or 1 or 2; each Hal is independently F or Cl; and each L is independently a C2-C18 alkyl group optionally including a heteroatom selected from oxygen or sulfur, or two or more L’s are connected together to form a C4-C30 (hetero)cyclic moiety.

13. The halophosphorane of claim 12, wherein one of Ri, R2, and R3 is PI / jHal, PHL2Hal, or PL2Hah, and the other two of Ri, R2, and R3 are each independently H, F, Cl, or CF3; each R4 is independently H or F; Y is O or S; R5 is (CF2)mCF3, with m being 0 or 1; n is 0 or 1; each Hal isF; and each Lis independently a C3-C12 alkyl group optionally including a heteroatom selected from oxygen or sulfur, or two or more L’s are connected together to form a C4-C30 (hetero)cyclic moiety.

14. The halophosphorane of claim 13, wherein one of Ri, R2, and R3 is PL3F, PHL2F, or PL2F2, and the other two of Ri, R2, and R3 are each independently H or F; each R4 is independently H or F; Y is O; R5 is CF3; n is 0 or 1; and each L is a C3-12 alkyl group or two or more L’s are connected together to form a C6-C20 (hetero)cyclic moiety.

15. The halophosphorane of claim 14, wherein one of Ri, R2, and R is PL3F, PHL2F, or PL2F2, and the other two of Ri, R2, and R3 are both F; each R4 is independently H or F; Y is O; R5 is CF3; n is 0 or 1; and each L is an isobutyl, an n-propyl, or an n-butyl group.

16. A composition comprising:a halophosphorane compound made by reaction of a trihydrocarbyl phosphine and a halogen-containing reactant, the halophosphorane compound comprising from 6 to 38 carbons, 4 to 26 of which carbons being non-halogenated and pendant from the phosphorous atom, at least one of the remaining 2 to 12 carbons comprising at least one pendant fluorine atom;an unreacted halogen-containing reactant comprising:2 to 12 carbon atoms;at least two halogen atoms, at least one of which is a fluorine atom;(a) at least one carbon-carbon double-bond, (b) no hydrogen atoms, or (c) both (a) and (b); andoptionally an oxygen or sulfur atom as an ether or thioether, respectively;a metalloid hydride source and / or a halogen-substituted metalloid compound; optionally a Lewis acid comprising a metal that comprises, consists essentially of, or is a transition metal from one or more of Groups 4, 5, 8, and 10 of the Periodic Table of Elements;optionally an organic solvent; and(i) less than 500 wppm of metals from Groups 6-7, 9, and 11-12 of the Periodic Table of Elements, (ii) less than 200 wppm of metals from Groups 6-7, 9, and 11-12 of the Periodic Table of Elements that do not originate as impurities from the optional organic solvent, or (iii) both (i) and (ii).

17. The composition of claim 16, wherein the metalloid hydride source, when present, comprises atri(Cl-C6 alkyl)fluorosilane, a mono-fluoro-tetra(Cl-C6 alkyl)disiloxane, adifluoro-tetra(Cl-C6 alkyl)disiloxane, a (C1-C6 alkyl)diarylfluorosilane, a di-(Cl-C6 alkyl)arylfluorosilane, or a mixture thereof, and wherein the halogen-substituted metalloid compound, when present, comprises atri(Cl-C6 alkyl)fluorosilane, 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, or a mixture thereof.

18. The composition of claim 16 or claim 17, wherein the 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, diphenylether, dibenzyl ether, diglyme, 0,0’-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, norbomane, adamantane, or a mixture thereof.

19. The composition of any of claims 16-18, comprising (i) less than 300 wppm of metals selected from the group consisting of Ag, Al, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof, (ii) less than 100 wppm of metals selected from the group consisting of Ag, Al, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof that do not originate as impurities from the optional organic solvent, or (iii) both (i) and (ii).

20. The composition of any of claims 16-18, comprising (i) less than 500 wppm of metals, (ii) less than 200 wppm of metals that do not originate as impurities from the optional organic solvent, or (iii) both (i) and (ii).

21. A composition comprising:a C2-C12 non-perhalogenated unsaturated product made by reaction of a trihydrocarbyl phosphine and a halogen-containing reactant, the C2-C12 non-perhalogenated unsaturated product comprising at least one fluorine atom and optionally an oxygen or sulfur atom as an ether or thioether, respectively;a trihydrocarbyl phosphine and / or a hydrocarbyl halophosphine;a metalloid hydride source and / or a halogen-substituted metalloid compound; optionally an organic solvent; and(i) less than 500 wppm of metals from Groups 6-7, 9, and 11-12 of the Periodic Table of Elements, (ii) less than 200 wppm of metals from Groups 6-7, 9, and 11-12 of the Periodic Table of Elements that do not originate as impurities from the optional organic solvent, or (iii) both (i) and (ii).

22. The composition of claim 21, wherein the C2-C12 non-perhalogenated unsaturated product comprises trifluoroethylene, chlorodifluoroethylene, difluoroethylene, hexafluoropropylene, pentafluoropropene, tetrafluoropropene, chloro-trifluoropropene, trifluoropropene, difluoropropene, vinyl fluoride, difluoro-(trifluoromethoxy)ethene, fluoro-(trifluoromethoxy)ethene, trifluoromethoxyethene, difluoromethoxyethene, fluoromethoxyethene, pentafluoro-l,3-butadiene, tetrafluoro- 1,3 -butadiene, trifluoro- 1,3-butadiene, difluoro-l,3-butadiene, pentafluorocyclobutene, tetrafluorocyclobutene, trifluorocyclobutene, difluorocyclobutene, fluorocyclobutene, heptafluorobutene, hexafluorobutene, pentafluorobutene, tetrafluorobutene, trifluorobutene, di fluorobutene, fluorobutene, heptafluorocyclopentene, hexafluorocyclopentene, pentafluorocyclopentene, tetrafluorocyclopentene, trifluorocyclopentene, difluorocyclopentene, fluorocyclopentene, nonafluoropentene, octafluoropentene, heptafluoropentene, hexafluoropentene, pentafluoropentene, tetrafluoropentene, trifluoropentene, difluoropentene, hexafluorodihydrothiophene, pentafluorodihydrothiophene, tetrafluorodihydrothiophene, trifluorodihydrothiophene, difluorodihydrothiophene, perfluoro(propenyl methyl ether), trifluoromethyl tetrafluoropropenyl ether, or a mixture thereof.

23. The composition of claim 21 or claim 22, wherein the trihydrocarbyl phosphine, when present, comprises, consists essentially of, or is a tri(C2-C18 alkyl) phosphine such as a tri(C3-C12 alkyl) phosphine, l,2-bis(dicyclohexylphosphino)ethane, 1,2-bis(dicyclopentylphosphino)ethane, l,2-bis(diisobutylphosphino)ethane, bis(2-dicyclohexylphosphinophenyl)ether (DCEphos), an n,n’-bis(diarylphosphino)alkane, an n,n’,n”-tris(diarylphosphino)alkane such as l,2-bis(diphenylphosphino)ethane (Diphos), 1,1’-bis(diphenylphosphino)ferrocene, l,l,l-tris(diphenylphosphinomethyl)ethane (Tripod), bis[2-(diphenylphosphino)ethyl]phenylphosphine (TriPhos), 9-isobutyl-9-phosphabicyclo[3.3.1 ]nonane; 9-isobutyl-9-phosphabicyclo[4.2.1 ]nonane; 9-n-butyl-9-phosphabicyclo[3.3.1]nonane; 9-n-butyl-9-phosphabicyclo[4.2.1]nonane; 1,2-bis(diisobutylphosphino)ethane; l,3-bis(diisobutylphosphino)propane; 2-n-butyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-n-hexyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-n-decyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-cyclohexylmethyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; 2-benzyl-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane; and 2-(3-hydroxyl-l-propyl)-4,8-dimethyl-2-phosphabicyclo[3.3.1]nonane, or a mixture thereof.

24. The composition of any of claims 21-23, wherein the trihydrocarbyl phosphine comprises, consists essentially of, or is a tri(C3-C6 alkyl) phosphine, for example a tri(C3-C4 alkyl) phosphine.

25. The composition of any of claims 21-24, wherein the metalloid hydride source, when present, comprises atri(Cl-C6 alkyl)fluorosilane, a mono-fluoro-tetra(Cl-C6 alkyl)di siloxane, a difluoro-tetra(Cl-C6 alkyl)disiloxane, a (C1-C6 alkyl)diarylfluorosilane, a di-(Cl-C6 alkyl)arylfluorosilane, or a mixture thereof, and wherein the halogen-substituted metalloid compound, when present, comprises atri(Cl-C6 alkyl)fluorosilane, 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, or a mixture thereof.

26. The composition of any of claims 21-25, wherein the 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, diphenylether, dibenzyl ether, diglyme, 0,0’-dimethyl-ethylene glycol, dimethyl acetamide (DMAc), dimethyl formamide (DMF), dimethyl sulfoxide (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, norbomane, adamantane, or a mixture thereof.

27. The composition of any of claims 21-26, comprising (i) less than 300 wppm of metals selected from the group consisting of Ag, Al, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof, (ii) less than 100 wppm of metals selected from the group consisting of Ag, Al, Co, Cr, Cu, Mn, Mo, Zn, and mixtures thereof that do not originate as impurities from the optional organic solvent, or (iii) both (i) and (ii).

28. The composition of any of claims 22-26, comprising (i) less than 500 wppm of metals, (ii) less than 200 wppm of metals that do not originate as impurities from the optional organic solvent, or (iii) both (i) and (ii).

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