Selective Preparation of Vinyl-Functionalized Chlorosilanes and Ethyl-Functionalized Chlorosilanes

Abstract

Disclosed is a method for preparing an organosilicon compound, which is carried out by subjecting ethylene to selective silylation. The method comprises reacting (A) a hydrosilane chloride compound and (B) ethylene in the presence of a catalyst (C) to carry out silylation, thereby preparing the organosilicon compound. The silylation can be selectively carried out as dehydrogenative coupling to prepare the organosilicon compound as a vinylchlorosilane compound, or as hydrosilylation to prepare the organosilicon compound as an ethylchlorosilane compound. The catalyst (C) contains a Ru(0) complex and can be recycled for subsequent silylation reactions without purification. Also disclosed is the organosilicon compound prepared according to the method.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims the benefit and all advantages of U.S. Provisional Patent Application No. 62 / 949,883, filed on December 18, 2019, and U.S. Provisional Patent Application No. 63 / 059,909, filed on July 31, 2020, the contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure generally relates to methods for preparing organosilicon compounds, and more particularly, to methods for selectively preparing vinylchlorosilanes and ethylchlorosilanes by tunable silylation.

[0004] Description of the Related Art

[0005] Hydrosilylation reactions are generally known in the art and involve an addition reaction between silicon - bonded hydrogen and an aliphatic unsaturated group. Hydrosilylation reactions are utilized in various applications, such as for cross - linking components of curable compositions. Hydrosilylation reactions can also be used to prepare individual components or compounds, such as components included in such curable compositions. Generally, hydrosilylation reactions are carried out in the presence of a platinum - metal - based catalyst due to its excellent catalytic activity and stability. Although platinum metals are generally more expensive than other metals with less catalytic activity, non - platinum catalysts suffer from instability when exposed to environmental conditions. Specifically, non - platinum catalysts may be prone to undesired side reactions with environmental oxygen and water, thus limiting their use and potential end - applications.

[0006] Similar to hydrosilylation reactions, dehydrogenative silylation reactions are also known in the art and similarly involve a reaction between silicon - bonded hydrogen and an aliphatic unsaturated group. However, in dehydrogenative silylation, instead of an addition reaction, the aliphatic unsaturated group is vinyl - bonded to silicon, with hydrogen gas (H2) produced as a by - product. Thus, dehydrogenative silylation reactions can be used to prepare unsaturated compounds (such as olefin - functional compounds), which can further undergo additional functionalization and / or coupling reactions (such as by hydrosilylation).

[0007] Unfortunately, the catalysts for dehydrogenative silylation suffer from many of the drawbacks associated with hydrosilylation catalysts, such as sensitivity to oxygen, water, and even light. In addition, while such drawbacks have been overcome by recent advances in hydrosilylation catalysts, many of the catalytic systems suitable for hydrosilylation reactions are not functional or practical for use in dehydrogenative silylation reactions. For example, many such catalysts exhibit selectivity in favor of the addition reaction, especially for the least substituted olefins, resulting in non-selective reactions with undesired product mixtures and low yields. Additionally, many conventional dehydrogenative silylation conditions are not tolerant of functional groups and are thus limited in their applications. SUMMARY OF THE INVENTION

[0008] The present disclosure provides a method for preparing an organosilicon compound. The method includes reacting (A) a hydrosilane chloride compound and (B) ethylene in the presence of a catalyst (C) comprising a Ru(0) complex to effect silylation, thereby preparing an organosilicon compound. The hydrosilane chloride compound (A) may have the general formula HSiCl x R 3-x , where the subscript x is 1, 2, or 3, and each R is an independently selected unsubstituted hydrocarbon group having from 1 to 18 carbon atoms. Optionally, silylation is employed as a dehydrogenative coupling or hydrosilylation reaction and can be used to prepare organosilicon compounds in the form of vinyl chloride silane compounds having the formula (H2CCH)SiCl x R 3-x or ethyl chloride silane compounds having the formula (CH3CH2)SiCl x R 3-x , where the subscripts x and R are as defined above. DETAILED DESCRIPTION

[0009] Also provided herein is a method for preparing an organosilicon compound (the "preparation method"). As will be understood from the description herein, the preparation method includes controlled ethylene silylation to selectively prepare organosilicon compounds with one or more ethylene-derived vinyl or ethyl groups. Silylation is achieved by using a conservative catalyst under adjustable conditions, which selectively promotes dehydrogenative coupling or hydrosilylation reactions, resulting in organosilicon compounds with the desired ethylene-derived functional groups. The specific materials and conditions employed also allow the catalyst to be recovered and recycled for subsequent silylation reactions without loss of activity or selectivity. Thus, the preparation method provides a unique platform for the efficient preparation of functionalized organosilicon compounds.

[0010] As will be understood by those skilled in the art, the vinyl or ethyl functional groups provided by silylation, along with other optional functional groups compatible with the conditions of the preparation method, provide organosilicon compounds that have numerous uses in countless compositions and methods, including the preparation of curable compositions (e.g., those based on one or more silicones) and their various components. For example, when vinyl-functionalized, the organosilicon compounds can be used in the preparation and / or crosslinking of curable compositions, such as starting materials, reagents, structural blocks, functionalized compounds, etc. When ethyl-functionalized, the organosilicon compounds can be used for different purposes in similar compositions and materials, such as end-capping agents or terminating agents, or for unique purposes, such as the preparation of low molecular weight silicones with reduced methyl content.

[0011] The preparation method comprises reacting (A) a hydrosilane compound with (B) ethylene in the presence of a catalyst (C) comprising a Ru(0) complex. The hydrosilane compound (A), ethylene (B), and the catalyst (C) containing the Ru(0) complex, as well as additional components that can be used in the preparation method, are further described below and may be collectively referred to herein as the "components" of the preparation method (i.e., "component (A)", "component (B)", "component (C)", etc., respectively), or equally collectively as "starting materials", "compounds", and / or "reagents" (A), (B), and / or (C), etc.).

[0012] As will be understood by those skilled in the art from the description herein, the preparation method prepares organosilicon compounds by silylation of components (A) and (B) catalyzed by catalyst (C), i.e., by forming silicon-bonded vinyl or ethyl in place of the silicon-bonded hydrogen atoms of the hydrosilane compound (A) ("reaction"). In this context, as used herein, the term "silylation" should be understood to encompass dehydrogenation and hydrosilylation coupling reactions, regardless of any specific reaction mechanism. In typical embodiments, as described below, the components and conditions of the silylation reaction employed in the preparation method are conservative across the two reaction types, such that general references to the reaction, components, conditions, etc. should be understood to apply to the preparation method as a whole. However, when the preparation method provides a choice between the two silylation mechanisms described above, the term "dehydrogenation coupling" is used herein to prepare vinyl-functional organosilicon compounds by dehydrogenative silylation of ethylene (B) with the hydrosilane compound (A). Similarly, the term "hydrosilylation" is used herein to prepare ethyl-functional organosilicon compounds by hydrosilylation of ethylene (B) with the hydrosilane compound (A).

[0013] As described above, component (A) is a hydrosilane compound, i.e., a silicone compound having at least one silicon-bonded hydrogen atom (i.e., Si-H group) and at least one silicon-bonded chlorine atom (i.e., Si-Cl group). The hydrosilane compound (A) is not otherwise particularly limited.

[0014] Generally, component (A) has the general formula HSiCl x R 3-x , where the subscript x is 1, 2, or 3, and each R is an independently selected hydrocarbyl group. In some embodiments, the hydrosilane compound (A) is further defined as an organohydrosilane such that in the above general formula the subscript x is 1 or 2. For example, in some such embodiments, the subscript x is 1 such that the hydrosilane compound (A) is further defined as a dihydrosilane having the formula HSiClR2. In other such embodiments, the subscript x is 2 such that the hydrosilane compound (A) is further defined as an organohydridodichlorosilane having the formula HSiCl2R. In alternative embodiments, the hydrosilane compound (A) is trichlorosilane (i.e., having the formula HSiCl3).

[0015] Regarding the formula of the organohydrosilane used above as component (A), each R is an independently selected hydrocarbyl group. Suitable hydrocarbyl groups can be substituted or unsubstituted. Regarding such hydrocarbyl groups, the term "substituted" describes a hydrocarbon moiety in which one or more hydrogen atoms are replaced by atoms other than hydrogen (e.g., halogen atoms such as chlorine, fluorine, bromine, etc.), carbon atoms within the hydrocarbon chain are replaced by atoms other than carbon (i.e., R can include one or more heteroatoms (oxygen, sulfur, nitrogen, etc.) within the carbon chain), or both. Thus, it should be understood that R can include or be a hydrocarbon moiety having one or more substituents (i.e., attached to and / or integral with its carbon chain / main chain) in its carbon chain / main chain such that R can contain or be an ether, an ester, etc.

[0016] Typically, the hydrocarbyl groups suitable for R can independently be straight-chain, branched-chain, cyclic, or combinations thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. The cyclic hydrocarbyl groups can independently be monocyclic or polycyclic. The straight-chain and branched-chain hydrocarbyl groups can independently be saturated or unsaturated. An example of a combination of a straight-chain and a cyclic hydrocarbyl group is an aralkyl group. General examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, etc., as well as their derivatives, modifications, and combinations. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, and, for example, branched-chain saturated hydrocarbyl groups having 6 to 18 carbon atoms. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Examples of suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl groups. However, it should be understood that in certain embodiments, the chemical nature of such alkenyl groups can participate in the silylation reaction. Thus, in certain embodiments, R does not contain or substantially does not contain olefin-containing functional groups. Examples of suitable monovalent halocarbon groups (i.e., hydrocarbyl groups) include haloalkyl groups, aryl groups, and combinations thereof. Examples of haloalkyl groups include alkyl groups in which one or more of the above hydrogen atoms are replaced by halogen atoms such as F or Cl. Specific examples of haloalkyl groups include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, as well as their derivatives. Examples of haloaryl groups include aryl groups in which one or more of the above hydrogen atoms are replaced by halogen atoms such as F or Cl. Specific examples of haloaryl groups include chlorobenzyl and fluorobenzyl groups. Typically, each R is an independently selected substituted or unsubstituted hydrocarbyl group. For example, in some embodiments, each R is independently selected from unsubstituted hydrocarbyl groups, such as straight-chain or unbranched unsubstituted hydrocarbyl groups. In a specific embodiment, each R is independently selected from unsubstituted hydrocarbyl groups having 1 to 18 carbon atoms.

[0017] When the subscript x is 1 such that the chlorosilane hydride compound (A) is further defined as dichlorosilane hydride, each R can be the same as or different from each other R in the chlorosilane hydride compound (A). In certain embodiments, each R is the same as each other R in the chlorosilane hydride compound (A). In other embodiments, one R is different from the other Rs in the chlorosilane hydride compound (A). In some embodiments, each R is an independently selected hydrocarbyl group having 1 to 18, alternatively 1 to 12, alternatively 1 to 6 carbon atoms. In certain embodiments, each R is independently selected from alkyl groups such as methyl group, ethyl group, etc. In a specific embodiment, each R is methyl. For example, in some such embodiments, the chlorosilane hydride compound (A) has the formula HSiCl x (CH3) 3-x , wherein the subscript x is as defined above. In certain such embodiments, component (A) includes dimethylchlorosilane (i.e., the formula HSiCl(CH3)2), methyldichlorosilane (i.e., the formula HSiCl2(CH3)) or a combination thereof.

[0018] Component (B) comprises ethylene, alternatively is ethylene. Ethylene is not limited and can be used in pure form (i.e., without or substantially without other components / compounds). In other words, component (B) can consist of ethylene, alternatively consist essentially of ethylene, alternatively can comprise a combination of ethylene and other components. For example, in some embodiments, the method includes introducing a reactor fluid into a vessel or reactor containing at least components (A) and (C), the reactor fluid comprising ethylene, alternatively consisting essentially of ethylene, alternatively consisting of ethylene. In such embodiments, the reactor fluid can comprise components other than ethylene such as a carrier medium which, as will be understood by those skilled in the art, will typically be or include a substance that is inert under the reaction conditions used in the preparation method (i.e., will not react with components (A), (B) or (C)). Examples of such carrier media include inert gases such as nitrogen (g) (N2), helium (g) (He), argon (g) (Ar), etc., and combinations thereof.) However, in certain embodiments, component (B) is used in pure form and consists essentially of ethylene (i.e., and is substantially free of carrier medium, alternatively free of carrier medium).

[0019] Ethylene can be used in gaseous form or as component (B). Thus, it should be understood that in certain embodiments, the preparation method is carried out in a vessel containing an ethylene atmosphere, as described in further detail below.

[0020] The preparation method can utilize any amounts of components (A) and (B), and more specifically, can include hydrosilane compounds (A) and ethylene (B) having different amounts or ratios, depending on the desired characteristics of the reaction, the specific organosilicon compound to be prepared, and / or the characteristics of the starting materials employed. As will be understood by those skilled in the art, components (A) and (B) are monofunctional with respect to the silylation reaction, such that the molar ratio (A):(B) and the stoichiometric ratio (A):(B) are the same. Thus, the theoretical maximum reaction of components (A) and (B) is achieved at a molar ratio of 1:1 (A):(B) (i.e., a 1:1 stoichiometric ratio of component (A) to component (B)). Therefore, the molar amount of ethylene used is typically at least equivalent to the molar amount of component (A) utilized. For example, components (A) and (B) can be used at a 1:1 (A):(B) molar ratio. An excess (e.g., a slight excess, a moderate excess, or an overall excess) of ethylene can also be utilized, as will be understood from the following description. Generally, components (A) and (B) are used at a molar ratio of 1:≥1 (A):(B), such as 1:1 to 1:100 (A):(B).

[0021] As described above, the silylation reaction of the preparation method can be adjusted to select for dehydrogenative coupling or hydrosilylation, and thereby prepare organosilicon compounds having vinyl functional groups or ethyl functional groups derived from ethylene, respectively (i.e., "reaction selectivity"). More specifically, the reaction selectivity can be controlled by the ratio of ethylene that is reactive in the reaction to the hydrosilane compound (A), i.e., the ratio between the amount of ethylene in the solution (i.e., dissolved ethylene) and the amount (e.g., concentration) of the hydrosilane compound (A) in the solution. As will be understood by those skilled in the art, the ethylene concentration in the liquid phase / reactivity phase of the reaction can be determined by direct measurement (e.g., using analytical techniques such as Raman spectroscopy, gas chromatography (GC)) or theoretical estimation (e.g., based on vapor-liquid equilibrium calculations) or any other technique known in the art.

[0022] Generally, the preparation method includes reacting components (A) and (B) at a stoichiometric ratio of at least 1:2 (A):(B) to prepare vinyl-functional organosilicon compounds by dehydrogenative coupling, or reacting components (A) and (B) at a stoichiometric ratio of less than 1:2 (A):(B) to prepare ethyl-functional organosilicon compounds by hydrosilylation. In other words, with all components and other reaction parameters being the same, the silylation is adjusted by changing the relative amount of ethylene available for reaction with the hydrosilane compound (A), where dehydrogenative coupling is favored at a relative ratio (B):(A) of 2 or higher (i.e., ≥2:1 (B):(A)), and hydrosilylation is favored at a relative ratio (B):(A) of less than 2 (i.e., <2:1 (B):(A)).

[0023] For example, in some embodiments, the silylation is further defined as the dehydrogenative coupling of a chlorosilane compound (A) and ethylene (B) such that an organosilicon compound is prepared as a vinylchlorosilane compound. In these embodiments, the dehydrogenative coupling is carried out at a stoichiometric ratio of the chlorosilane compound (A) to ethylene (B) of at least 1:2, alternatively at least 1:3 (A):(B). For example, in certain embodiments, ethylene is used in an amount sufficient to provide a molar ratio of ethylene (B) to chlorosilane compound (A) of from 2:1 to 100:1, such as from 2:1 to 50:1, alternatively from 2:1 to 25:1, alternatively from 2:1 to 20:1, alternatively from 2:1 to 15:1, alternatively from 2:1 to 10:1, alternatively from 2:1 to 6:1, alternatively from 3:1 to 6:1 (B):(A). It should be understood that ratios outside of these ranges may also be utilized.

[0024] Generally, the specific amounts of components (A) and (B) that react by dehydrogenative coupling will be selected based on the desired organosilicon compound to be prepared and optionally its desired end use. For example, in certain embodiments, the ratio of components (A) and (B) is selected to provide a dehydrogenative coupling reaction in which the conversion of the chlorosilane compound (A) to the vinylchlorosilane compound is at least 75%, such as a conversion of at least 80%, alternatively at least 85%, alternatively at least 90%, alternatively at least 95%, alternatively at least 98%. In some such embodiments, the dehydrogenative coupling reaction also comprises a yield of at least 75% of the organosilicon compound (e.g., vinylchlorosilane compound), such as a yield of at least 80%, alternatively at least 85%, alternatively at least 90%, alternatively at least 95%.

[0025] In certain embodiments, the silylation is further defined as the hydrosilylation of a chlorosilane compound (A) and ethylene (B) such that an organosilicon compound is prepared as an ethylchlorosilane compound. In these embodiments, the hydrosilylation is carried out at a stoichiometric ratio of the chlorosilane compound (A) to ethylene (B) of less than 1:2 (A):(B). For example, in certain embodiments, ethylene is used in an amount sufficient to provide a molar ratio of ethylene (B) to chlorosilane compound (A) of from 1:1 to less than 2:1, such as greater than 1:1 to less than 2:1, alternatively greater than 1:1 to 1.9:1 (B):(A). Higher or lower ratios may also be used, e.g., depending on the reaction components and parameters selected, desired reaction selectivity / yield, etc.

[0026] Typically, the specific amounts of components (A) and (B) that react via hydrosilylation will be selected based on the desired organosilicon compound to be prepared and optionally its desired end use. In certain embodiments, the ratio of components (A) and (B) is selected to provide a hydrosilylation reaction in which the conversion of the hydrosilane chloride compound (A) to the ethylchlorosilane compound is at least 75%, such as at least 80%, alternatively at least 85%, alternatively at least 90%, alternatively at least 95%, alternatively at least 98%. In some such embodiments, the hydrosilylation reaction also includes a yield of at least 75% of the organosilicon compound (e.g., ethylchlorosilane compound), such as at least 80%, alternatively at least 85%, alternatively at least 90%, alternatively at least 95%.

[0027] Typically, the specific amounts of components (A) and (B) will be selected based on the desired organosilicon compound to be prepared and optionally its desired end use. For example, in certain embodiments, the ratio of components (A) and (B) is selected to provide a dehydrogenative coupling reaction in which the conversion of the hydrosilane chloride compound (A) to the vinylchlorosilane compound is at least 75%, such as at least 80%, alternatively at least 85%, alternatively at least 90%, alternatively at least 95%, alternatively at least 98%. In some such embodiments, the dehydrogenative coupling reaction also includes a yield of at least 50% of the organosilicon compound (e.g., vinylchlorosilane compound), such as at least 60%, alternatively at least 65%, alternatively at least 70%, alternatively at least 75%.

[0028] As described above, component (C) is a catalyst and more specifically a catalyst comprising a Ru(0) complex, i.e., a complex containing ruthenium (Ru) in a neutral oxidation state. The Ru(0) complex is not particularly limited and can be any Ru(0) complex capable of catalyzing the silylation of ethylene with the hydrosilane chloride compound (A).

[0029] Examples of suitable Ru(0) complexes include {Ru(η 4 -1,5-COD)(η 6 -1,3,5-COT)}; {Ru(PPh3)3(CO2)}; {Ru(η 4 -1,5-COD)(η 6 -triphenylene)}; {[Ru(η 4 -1,5-COD)]2(η 12 -triphenylene)}; {Ru(η 4 -1,5-COD)(η 4 -1,3-COT)PR’3}; {Ru(η 6 -1,3,5-COT)PR’3}; {Ru(η4 -1,5-COD)(PR’3)3}; {Ru(η 4 -1,5-COD)(tBuNC)3}; {[Ru(η 4 -1,5-COD)]3(η 18 -triphenylene)}; [Ru3(CO) 10 (MeCN)2]; Ru3(CO) 12 ; etc., as well as their derivatives, modifications, and combinations. Those skilled in the art will understand that the ligands represented by COD and COT are cyclooctadiene and cyclooctatriene, respectively. The ligand represented by the general formula PR’3 is a tertiary phosphine compound (such as phosphine, phosphite, etc.), where each R' is an independently selected substituted or unsubstituted aryl group, aralkyl group, or cycloalkyl group, or their corresponding alkoxy or aryloxy groups, as exemplified by those described herein.

[0030] In certain embodiments, the Ru(0) complex includes a triruthenium complex or its derivatives. Examples of triruthenium complexes include {[Ru(bda)-(pic)2(μ-O)]2Ru(pic)2(H2O)2} 2+ ; {[Ru3(μ-H)(μ-η 3 -dpa-C,N,N)(CO)9}; {(Ru(acac)2)3(diquinoxaline[2,3-a:2’,3’-c]phenazine)}; {[Cp*Ru(μ-H)]3(μ3-η 2 -(II)-PhCCH)(μ3-BH)}; [Ru3(dmbpy)6(μ-HAT)] 6+ ; {[Ru(η 4 -1,5-COD)]3(η 18 -triphenylene)}; [Ru3(CO) 10 (MeCN)2]; Ru3(CO) 12 ; etc., as well as their derivatives, modifications, and combinations. Those skilled in the art will understand that the ligands represented by bda, pic, dpa, acac, dmbpy, and HAT are 2,2-bipyridine-6,6-dicarboxylate, 2-aminomethylpyridine, diaminomethylpyridine, acetylacetonate, 4,4'-dimethyl-2,2'-bipyridine, and 1,4,5,8,9,12-hexaoxatriphenylene or their deprotonated forms, respectively.

[0031] As will be appreciated from the above exemplary complexes and the further description and examples below, the Ru(0) complex may include a phosphorus ligand. Examples of phosphorus ligands include phosphines, phosphites, phosphates, phosphine oxides, phosphinamides, phosphonium salts, phosphinamines, chlorophosphines, phosphimines, phosphorodiamides, phosphinites, phosphonates, phosphonites, triaminophosphines, trimethylsilylphosphines, etc., as well as their derivatives, modifications, and combinations. Those skilled in the art will understand that such ligands may be utilized in ionic form (e.g., from protonation / deprotonation), which ionic forms are encompassed by the above examples and illustrated in various embodiments herein. Specific examples of phosphorus ligands include phosphines, trimethylphosphine, triphenylphosphine, methyldiphenylphosphine, trifluorophosphine, trimethyl phosphite, triphenyl phosphite, tricyclohexylphosphine, dimethylphosphinomethane (dmpm), dimethylphosphinoethane (dmpe), diphenylphosphinomethane (dppm), diphenylphosphinoethane (dppe), S,S-chiraphos, ethane-1,2-diylbis[(2-methoxyphenyl)phenylphosphane] (DIPAMP), 1,1'-bis(diphenylphosphino)ferrocene (dppf), tris(o-tolyl)phosphine, (2,4,6-triisopropylphenyl)dicyclopentylphosphine, etc., as well as their derivatives, modifications, and combinations. Those skilled in the art will understand that such phosphorus ligands include the phosphite forms of the above phosphines, as well as homosubstituted and heterosubstituted phosphines and phosphites having any one or more of the phosphorus-bonding groups exemplified herein.

[0032] In a specific embodiment, the Ru(0) complex of catalyst (C) includes a phosphorus ligand having the general formula R 1 3P, where each R 1 is an independently selected hydrocarbyl group. Examples of suitable hydrocarbyl groups include the hydrocarbyl groups set forth above with respect to R. As will be understood by those skilled in the art, each R 1 may be independently selected based on factors such as steric hindrance, electronics (e.g., electron-donating effect, inductive effect, or electron-withdrawing effect), or combinations thereof. Each R 1 may be selected to impart chirality or symmetry to the catalyst. In these or other embodiments, R 1 may be independently selected to effect regioselectivity of reactivity, such as anti-Markovnikov selectivity (e.g., such as when ethylene is substituted). In certain embodiments, each R 1 is independently a branched or cyclic group; for example, each R 1 may be independently selected from isopropyl, isobutyl, tert-butyl, other branched alkyls, aryls, alkaryls, aralkyls, substituted aryls (e.g., pentafluorophenyl, etc.), etc. In a specific embodiment, each R 1are the same. In some embodiments, the phosphorus ligand has the formula R 1 2PR 2 , where R 1 is as defined above and R 2 is R 1 or a phosphorus-containing (i.e., substituted) hydrocarbyl group such that the phosphorus ligand is a polydentate ligand having more than one phosphorus atom. Specific examples of such phosphorus ligands include 1,3-bis(dicyclohexylphosphino)propane and 1,3-bis(diphenylphosphino)propane. In a specific embodiment, the phosphorus ligand is further defined as an organophosphine ligand. In some such embodiments, each R 1 is an independently selected substituted or unsubstituted aryl group, aralkyl group, or cycloalkyl group, and R 2 is R 1 or an alkaryl group. Examples of such organophosphine ligands include substituted and unsubstituted triarylphosphines, tricycloalkylphosphines, bis(diarylphosphino)alkanes, bis(dicycloalkylphosphino)alkanes, and combinations thereof.

[0033] In a specific embodiment, the Ru(0) complex of the catalyst (C) comprises an organic phosphite ligand, such as those having the formula (R 1 O)2P(OR 2 ), where R 1 and R 2 are as defined above. In some such embodiments, each R 1 and R 2 comprises a substituted or unsubstituted aryl group such that the organic phosphite ligand is further defined as a triaryl phosphite ligand.

[0034] Additional examples of suitable phosphorus ligands include those having intermediate Tolman Electronic Parameter (TEP) and / or intermediate Tolman Cone Angle (TCA). For example, in some embodiments, the Ru(0) complex of the catalyst (C) includes a TEP of 2,050 to 2,100 cm -1 , such as 2,060 to 2,090, alternatively 2,065 to 2,085 cm -1phosphorus ligand. In these or other embodiments, the Ru(0) complex comprises a phosphorus ligand with a TCA of 100 to 200 °, such as 115 to 185 °, alternatively 130 to 170 °. As will be understood by those skilled in the art, the TEP of the phosphorus ligand is based on the A1-symmetric CO stretching frequency (ω) of the standard nickel tricarbonyl complex (i.e., having the formula (R’3P)Ni(CO)3, where the ligand PR’3 is the phosphorus ligand, incorporated as defined above), and the vibrational spectrum (i.e., infrared (IR) spectrum or Raman spectrum) of the complex can be measured according to the following relationship: TEP = ω(CO,Ni; A1) = 2056.1 + pL, where pL is the ligand-specific increment of the CO stretching frequency (ω). Typically, P(tBu)3 is used as a reference, where pL(P(tBu)3) is set to 0, such that ω(CO,A1) = 2056.1 cm -1 . As will also be understood by those skilled in the art, the TCA of the phosphorus ligand in a transition metal complex is the solid angle formed with the metal at the vertex, and the outermost edge / perimeter of the cone is minimized around the van der Waals sphere of the ligand atoms, and can be determined using computational space-filling models and / or empirical bonding characterizations. Methods and materials for such determinations of TEP and / or TCA are more elaborated in Tolman, Chemical Reviews, 1977, vol 77(3) pp 313-348, the characterization methods and phosphorus ligands of which are incorporated herein by reference.

[0035] The specific phosphorus ligand used in the Ru(0) complex of the catalyst (C) can be selected based on the specific hydridosilane compound (A) utilized and / or the specific organosilicon compound to be prepared. For example, in certain embodiments, the reaction components / parameters are selected to prepare a vinyl-functional organosilicon compound (e.g., by dehydrogenative coupling of components (A) and (B)), the hydridosilane compound (A) is an organohydridosilane, and the Ru(0) complex of the catalyst (C) comprises a phosphorus ligand. In some such embodiments, the hydridosilane compound (A) is an organohydridosilane having the formula HSiClR2, and the Ru(0) complex of the catalyst (C) comprises an organophosphine ligand. In other embodiments, the hydridosilane compound (A) is an organodichlorosilane having the formula HSiCl2R, and the Ru(0) complex of the catalyst (C) comprises an organophosphite ligand.

[0036] In a specific embodiment, the Ru(0) complex comprises dodecacarbonyl (i.e., of the formula Ru3(CO) 12) or its derivatives), alternatively the dodecacarbonyl. In some such embodiments, the dodecacarbonyl ruthenium derivative is further defined as a ligand exchange derivative of dodecacarbonyl ruthenium having one or more phosphorus ligands. In a specific embodiment, one or more of the phosphorus ligands are selected from phosphines and phosphites, such as any of those described herein. It is understood that such ligand exchange derivatives can also be prepared from ruthenium compounds / complexes other than dodecacarbonyl ruthenium and are encompassed by the scope of the Ru(0) complexes herein, regardless of whether they are prepared from dodecacarbonyl ruthenium or another ruthenium compound / complex or otherwise obtained.

[0037] The Ru(0) complex can include other ligands in addition to those described above, such as those containing and / or derived from amines, ketones, diketones, olefins, nitriles, carbenes, etc. and combinations thereof. The additional ligands can be prepared in situ (i.e., during the preparation method), for example, by solvent exchange and / or normal catalytic operations of the Ru(0) complex in the presence of components (A) and (B), as will be understood from the further description below regarding catalyst residues and separation / recycling / reuse of catalyst residues.

[0038] The Ru(0) complex of catalyst (C) can be used in any form, such as in pure form (i.e., in the absence of solvents, carrier media, diluents, etc.), or disposed in a carrier medium, such as a solvent or dispersant (e.g., any of those listed and / or described herein), which will be independently selected by those skilled in the art (e.g., based on the specific component (A) selected, the solubility of the Ru(0) complex, etc.). Thus, catalyst (C) can consist of the Ru(0) complex, alternatively consist essentially of the Ru(0) complex, or alternatively can include additional components, such as carrier media, diluents, etc.

[0039] Catalyst (C) can be used in any amount, which will be selected by those skilled in the art, for example, based on the specific catalyst (C) selected (e.g., the concentration / amount of its active Ru species), the nature / type of the selected component (A), the reaction parameters employed, the scale of the reaction (e.g., the total amount of component (A) used), etc. The molar ratio of catalyst (C) to component (A) and / or (B) used in the reaction can affect the rate and / or amount of the silylation of the organosilane compound to be prepared. Thus, the amount of catalyst (C) and the molar ratio between them can vary compared to component (A) and / or component (B). Generally, these relative amounts and molar ratios are selected to maximize the reaction of components (A) and (B) while minimizing the loading of catalyst (C) (e.g., to increase the economic efficiency of the reaction, increase the ease of purification of the reaction product formed, etc.).

[0040] In certain embodiments, the catalyst (C) is used in an amount of from 0.000001 to 50 wt.% (i.e., wt. / wt.) based on the total amount of component (A) used. For example, the catalyst (C) can be used in an amount of from 0.000001 to 25 wt.%, alternatively from 0.00001 to 10 wt.%, alternatively from 0.0001 to 5 wt.% based on the total amount of component (A) used. In some embodiments, the catalyst (C) is used in an amount sufficient to provide a ratio of Ru(0) complex to hydrosilane compound (A) of from 1:10 to 1:1,000,000, alternatively from 1:50 to 1:1,000, alternatively from 1:100 to 1:500 (C):(A). Such ratios can be weight ratios (i.e., wt. / wt.((C):(A), alternatively their active components), or molar ratios (C):(A), alternatively their active components. It should be understood that amounts and ratios outside the ranges listed above can also be employed. For example, the catalyst (C) can be used in a stoichiometric amount (i.e., supra-catalytic amount) based on the total amount of component (B) (i.e., its ethylene) used in the preparation method.

[0041] It should be understood that the catalyst (C) can comprise a combination of different Ru(0) complexes, such as 2, 3, 4, 5 or more Ru(0) complexes, which can be the same as or different from any other Ru(0) complex of the catalyst (C) (e.g., in terms of ligand identity, geometry, ruthenium content, etc.).

[0042] The catalyst (C) and / or its Ru(0) complex can be prepared or otherwise obtained (i.e., as a prepared compound). Methods for preparing many of the above-exemplified Ru(0) complexes are known in the art, using compounds commercially available from various suppliers. Thus the catalyst (C) can be prepared prior to the reaction of components (A) and (B) or prepared in situ (i.e., during the reaction of components (A) and (B), e.g., by combining the components of the catalyst (C) with components (A) and / or (B)).

[0043] In certain embodiments, the catalyst (C) is prepared as part of the preparation method, i.e., the preparation method includes preparing the catalyst (C). Preparing the catalyst (C) can include preparing the Ru(0) complex or providing the Ru(0) complex in a form suitable for catalyzing the hydrosilylation of components (A) and (B).

[0044] In a specific embodiment, the preparation method includes preparing a Ru(0) complex to obtain catalyst (C). In such embodiments, preparing the Ru(0) complex generally includes optionally combining a catalyst precursor compound and a ligand precursor compound in the presence of a support medium to obtain a Ru(0) complex (e.g., by ligand exchange), which can be directly used in the reaction of components (A) and (B) (e.g., directly used as catalyst (C)), or alternatively, can be purified, treated, combined with a support medium, or otherwise modified to prepare catalyst (C). However, it should be understood that preparing the Ru(0) complex can include any number of additional steps / processes / procedures described in further detail below, such as oxidizing or reducing ruthenium complexes / compounds with different oxidation states to obtain the Ru(0) complex.

[0045] Examples of catalyst precursor compounds generally include Ru(0) complexes and triruthenium complexes (including those described above) and their derivatives, modifications, and combinations. For example, in certain embodiments, the catalyst precursor compound is dodecacarbonyltriruthenium. Examples of ligand precursor compounds include the phosphorus ligands described above, including their protonated and / or salt forms. For example, in certain embodiments, the ligand precursor compound is a tertiary phosphorus compound. In some such embodiments, the tertiary phosphorus compound is an organophosphine compound having the formula R 1 2PR 2 , where R 1 and R 2 are as defined above. In other such embodiments, the tertiary phosphorus compound is an organophosphite compound having the formula (R 1 O)2P(OR 2 ), where R 1 and R 2 are as defined above.

[0046] The catalyst and ligand precursor compounds can be provided, prepared, or otherwise obtained (e.g., obtained from a commercial source). In certain embodiments, preparing catalyst (C) further includes preparing the catalyst and / or ligand precursor compounds before and / or simultaneously with complexing the ruthenium of the catalyst precursor compound with the ligand precursor compound to obtain the Ru(0) complex. As understood in the art, the catalyst and ligand precursor compounds can be prepared or synthesized by a variety of routes or techniques.

[0047] As described above, the Ru(0) complex can be prepared in a support medium, such as any of those described herein. For example, the Ru(0) complex can be prepared in a medium in which the catalyst (C) is disposed during use. In certain embodiments, the Ru(0) complex is prepared in the presence of an aromatic solvent (e.g., an aromatic organic solvent), such as benzene, toluene, xylene (e.g., o-xylene, m-xylene, and / or p-xylene), mesitylene (i.e., 1,3,5-trimethylbenzene), etc. or a combination thereof. Depending on various options, when the catalyst (C) is prepared and / or disposed in a medium or solvent, the medium or solvent or a portion thereof can complex with Ru(0), e.g., become a ligand or other component of the Ru(0) complex.

[0048] In a specific embodiment, preparing the catalyst (C) includes combining a catalyst and a ligand precursor compound in the presence of an aromatic solvent, thereby preparing the Ru(0) complex in the aromatic solvent. Generally, the catalyst and the ligand precursor compound and the aromatic solvent are combined in a vessel or reactor to prepare the Ru(0) complex and / or the catalyst (C). The vessel or reactor can be heated or cooled in any suitable manner, such as a jacket, a shroud, an exchanger, a bath, a coil, etc. For example, in some embodiments, the catalyst and the ligand precursor compound are combined in an aromatic solvent at a high temperature to obtain the Ru(0) complex and thus prepare the catalyst (C). The high temperature used to prepare the catalyst (C) will depend on the specific catalyst and / or ligand precursor compound selected, the specific aromatic solvent used and / or other support carriers, the reaction vessel selected (e.g., whether open to ambient pressure, sealed, under reduced pressure, etc.), etc. Thus, one of ordinary skill in the art will select the high temperature used to prepare the catalyst (C) based on the reaction conditions and parameters selected and the description herein. The high temperature used to prepare the catalyst (C) is generally greater than ambient temperature to 300 °C, such as 50 °C to 250 °C, alternatively 60 °C to 200 °C, alternatively 70 °C to 175 °C, alternatively 75 °C to 150 °C, alternatively 80 °C to 125 °C. High temperatures outside of these ranges can also be utilized.

[0049] In certain embodiments, the preparation method includes reacting components (A) and (B) in the presence of an (D) olefin compound. As will be understood by one of ordinary skill in the art, the olefin compound (D) is generally used in embodiments where the reaction components / parameters are selected to prepare a vinyl-functionalized organosilicon compound (e.g., by dehydrogenative coupling of components (A) and (B)). The olefin compound (D) contains an unsaturated aliphatic hydrocarbon group, which can also be referred to as an aliphatic unsaturated group, an ethylenically unsaturated group, etc., depending on the specific form of the hydrocarbon group having the unsaturation (e.g., C-C double bond and / or triple bond) and is not otherwise particularly limited.

[0050] Typically, the olefin compound (D) contains at least one aliphatic unsaturated group per molecule. However, in certain embodiments, the olefin compound (D) contains an average of at least two aliphatic unsaturated groups per molecule. Of course, the olefin compound (D) may also contain any number of additional aliphatic unsaturated groups. Each aliphatic unsaturated group of the olefin compound (D) can be a terminal, side chain, or both positions in the olefin compound (D), for example depending on its structure.

[0051] In certain embodiments, the olefin compound (D) contains an organic compound, alternatively an organic compound. In other embodiments, the olefin compound (D) contains a siloxane, alternatively a siloxane. In still other embodiments, the olefin compound (D) contains a silicone-organic hybrid or an organosilicon compound, alternatively a silicone-organic hybrid or an organosilicon compound. Various embodiments and examples of the olefin compound (D) are further disclosed below.

[0052] The aliphatic unsaturated groups of the olefin compound (D) can be alkenyl groups and / or alkynyl groups. As will be understood by those skilled in the art, the term "alkenyl group" refers to a group having one or more carbon-carbon double bonds (e.g., an olefin), and the term "alkynyl group" refers to a group having one or more carbon-carbon triple bonds (e.g., an alkyne). Any of such groups can be cyclic or acyclic, branched or unbranched, substituted or unsubstituted, and combinations thereof. Such groups generally have no limitations in terms of size and / or overall structure other than the olefin moiety, and can contain, for example, 2 to 30 carbon atoms, such as 2 to 24 carbon atoms, alternatively 2 to 20, alternatively 2 to 12, alternatively 2 to 10, alternatively 2 to 6 carbon atoms. Specific alkenyl groups are exemplified by vinyl, vinylene, allyl, propenyl, and hexenyl groups. Suitable alkenyls include internal alkenyls, external alkenyls, terminal alkenyls (e.g., α-olefins), poly-substituted alkenyls (e.g., cis- and trans-disubstituted, trisubstituted, and tetrasubstituted olefins), and combinations thereof. Examples of specific alkynyl groups include ethynyl, propynyl, and butynyl groups.

[0053] Examples of compounds suitable as the olefin compound (D) include alkenyl compounds (e.g., compounds having at least one alkenyl group), such as butene (e.g., isobutene, cyclobutene, etc.), pentene (e.g., 4-methyl-1-pentene, 3-methyl-1-pentene, cyclopentene, 2-methylcyclopentene, 4-methylcyclopentene, etc.), hexene (e.g., cyclohexene, 3,5,5-trimethyl-1-hexene, vinylcyclohexene, etc.), linear α-olefins (e.g., 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, etc.), cyclic olefins (e.g., cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, vinylnorbornane, etc.), polyolefins (e.g., 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,5-divinylcyclohexane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1,3-dienylcyclopentane, dicyclopentadiene, norbornadiene, etc.), branched acyclic olefins (e.g., 5-methyl-1-nonene), olefin-substituted cyclic compounds (e.g., vinylcyclohexane, etc.), linear and cyclic alkyne compounds, diene compounds (e.g., 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene, 1,19-eicosadiene, etc.), diyne and enyne compounds (e.g., 1,3-butadiyne, 1,5-hexadiyne, 1-hexen-5-yne, etc.), etc., as well as their derivatives, modifications, and combinations. The specific aliphatic unsaturated groups and / or compounds used or used as the olefin compound (D) will generally be selected based on the hydrogenation and / or hydrosilylation rate. For example, in certain embodiments, the olefin compound (D) is selected to readily undergo hydrogenation but slowly undergo hydrosilylation. In certain embodiments, the olefin compound (D) comprises norbornene or its derivatives or analogs, alternatively consists essentially of them, alternatively consists of them.

[0054] The preparation method can utilize any amount of component (D), and more specifically, can include any amount and / or ratio of its olefin compounds, which depends on the desired characteristics of the reaction (such as conversion rate, etc.) and / or the characteristics of the starting materials used. Generally, component (D) is used in an amount sufficient to provide an olefin compound in a stoichiometric ratio of at least 1:1 based on the number of silicon-bonded hydrogen groups of component (A) to be vinylated (i.e., the number of Si-H groups capable of undergoing dehydrogenative coupling reaction). Therefore, the amount of component (D) is usually selected based on the amount and type of the chlorosilane compound (A), as will be understood by those skilled in the art. An excess or overall excess of component (D) can be utilized. For example, components (A) and (D) can be utilized in a stoichiometric ratio of 1:≥1 (A):(D), such as a ratio of 1:1 to 1:100 (A):(D). In certain embodiments, component (D) is used in an amount sufficient to provide a molar ratio of olefin compound to chlorosilane compound (A) of 1:1 to 100:1 (D):(A), such as 1:1 to 10:1, alternatively 2:1 to 10:1, alternatively 3:1 to 5:1 (D):(A). Higher or lower ratios can also be used.

[0055] The components used in the preparation method (i.e., the chlorosilane compound (A), ethylene (B), catalyst (C), and / or olefin compound (D) (when used)) can be provided "as is", i.e., ready to react to prepare the organosilicon compound. Alternatively, any one or more or all of components (A), (B), (C), and / or (D) can be formed before or during the reaction (for example, such as in the case where the method includes preparing the catalyst (C), as described above). In some embodiments, the preparation method further includes preparing the chlorosilane compound (A). In these or other embodiments, the preparation method further includes preparing ethylene (B). In these or other embodiments, the preparation method further includes preparing the catalyst (C). In these or other embodiments, the preparation method further includes preparing the olefin compound (D).

[0056] Generally, components (A), (B), (C), and optionally (D) react in a container or reactor to prepare the organosilicon compound. When the reaction is carried out at an elevated or reduced temperature as described below, the container or reactor can be heated or cooled in any suitable manner, such as by a jacket, shroud, exchanger, bath, coil, etc.

[0057] Components (A), (B), (C) and optionally component (D) can be fed into a container together or separately, or can be arranged in the container in any order of addition and any combination. For example, in certain embodiments, components (A), (B) and (D) are added to a container containing component (C), for example as a preformed catalyst, or as separate components for in-situ formation of catalyst (C). In a specific embodiment, catalyst (C) is prepared in a container, and then components (A) and optionally (D) are charged into the container to prepare a solution in the container, and then pressurized with component (B). In some embodiments, components (A) and (D) can be combined prior to being added to the container, or can be added to the container sequentially (e.g., (A) is added first and then (D)). Generally speaking, the reference to "reaction mixture" herein usually refers to a mixture containing components (A), (B) and (C) and optionally (D) (if used) (e.g., obtained by combining such components as described above).

[0058] The method can also compare stirring the reaction mixture. When combined, for example, in its reaction mixture, stirring can enhance the mixing and contact of components (A), (B), (C) and optionally (D) together. Such independent contact can employ other conditions, with stirring (e.g., simultaneously or sequentially) or without stirring (i.e., independent of stirring, or instead of stirring). Other conditions can be customized to enhance the contact between the chlorosilane compound (A) and ethylene (B) and thus enhance their reaction (i.e., silylation) to form a silicone compound. Other conditions can be conditions effective for increasing the reaction yield or minimizing the amount of specific reaction by-products included in the reaction product relative to the silicone compound.

[0059] Components (A) and (B) can react in the presence of a carrier medium (such as a solvent, diluent, fluid or a combination thereof), such that the reaction proceeds in a solution, emulsion, suspension, slurry, two-phase mixture or a combination thereof. The specific solvent, carrier and / or diluent utilized and their respective amounts will be independently selected by those skilled in the art, for example based on the specific chlorosilane compound (A), catalyst (C) and / or olefin compound (D) (when used), the specific silicone compound to be prepared, etc. Generally, the reaction is carried out under homogeneous conditions (e.g., in a solution state). However, the reaction can be carried out heterogeneously, for example with one or more components suspended but not dissolved in the carrier medium. Generally, ethylene (B) is used in gaseous form, for example at a pressure selected to prepare a reaction mixture having a desired molar ratio of (A):(B), and thus giving the desired reaction chemistry. However, other components can be used as a homogeneous mixture / solution (i.e., dissolved and / or set in the carrier medium prior to forming the reaction mixture).

[0060] In certain embodiments, the reaction is carried out in the presence of a carrier medium. The carrier medium is not particularly limited and is generally selected based on the particular chlorosilane compound (A), catalyst (C), and / or olefin compound (D) (when used) and the particular silicone compound to be prepared. For example, in such embodiments, the carrier medium generally includes oils (such as organic oils and / or silicone oils), fluids, solvents, etc. or combinations thereof, alternatively oils (such as organic oils and / or silicone oils), fluids, solvents, etc. or combinations thereof.

[0061] In some embodiments, the carrier medium comprises an organic solvent, alternatively an organic solvent. Examples of organic solvents include those containing aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as heptane, hexane, and octane; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, and dichloromethane; chloroform; dimethyl sulfoxide; dimethylformamide, acetonitrile; tetrahydrofuran; petroleum solvents; solvent naphtha; naphtha; N-methylpyrrolidone; etc., as well as their derivatives, modified products, and combinations.

[0062] In some embodiments, the carrier medium comprises a silicone fluid, alternatively a silicone fluid. The siloxane fluid is generally a low-viscosity and / or volatile siloxane. In some embodiments, the siloxane fluid is a low-viscosity organopolysiloxane, a volatile methyl siloxane, a volatile ethyl siloxane, a volatile methyl ethyl siloxane, etc., or combinations thereof. Generally, the siloxane fluid has a viscosity in the range of 1 to 1,000 mm 2 / s at 25°C. Specific examples of suitable siloxane fluids include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethyl-3-{[(trimethylsilyl)oxy]}trisiloxane, hexamethyl-3,3-bis{[(trimethylsilyl)oxy]}trisiloxane, pentamethyl{[(trimethylsilyl)oxy]}cyclotrisiloxane, and polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, octylpolymethylsiloxane, hexamethyldisiloxane, heptamethyloctyltrisiloxane, hexylpolymethyltrisiloxane, etc., as well as their derivatives, modified products, and combinations. Additional examples of suitable silicone fluids include polyorganosiloxanes having a suitable vapor pressure (such as 5×10 -7 to 1.5×10 -6 m 2 / s).

[0063] In certain embodiments, the carrier vehicle comprises an organic fluid, alternatively an organic fluid, which generally includes an organic oil comprising volatile and / or semi-volatile hydrocarbons, esters, and / or ethers. General examples of such organic fluids include volatile hydrocarbon oils such as C6-C 16 alkanes, C8-C 16 isoparaffins (e.g., isodecane, isododecane, isohexadecane, etc.), C8-C 16 branched esters (e.g., isohxyl neopentanoate, isodecyl neopentanoate, etc.), and the like, as well as their derivatives, modifications, and combinations. Additional examples of suitable organic fluids include aromatic hydrocarbons, aliphatic hydrocarbons, alkyl halides, aromatic halides, and combinations thereof. Hydrocarbons include isododecane, isohexadecane, isohexadecane L (C 11 -C 13 ), isohexadecane H (C 11 -C 12 ), hydrogenated polydecene.

[0064] Other carrier vehicles can also be used in the composition. For example, in some embodiments, the carrier vehicle comprises an ionic liquid, alternatively an ionic liquid. Examples of ionic liquids include anion-cation combinations. Generally, the anion is selected from alkyl sulfate-based anions, tosylate anions, sulfonate-based anions, bis(trifluoromethanesulfonyl)imide anions, bis(fluorosulfonyl)imide anions, hexafluorophosphate anions, tetrafluoroborate anions, etc., and the cation is selected from imidazolium-based cations, pyrrolidinium-based cations, pyridinium-based cations, lithium cations, etc. However, combinations of various cations and anions can also be utilized. Specific examples of ionic liquids generally include 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis-(trifluoromethanesulfonyl)imide, 3-methyl-1-propylpyridinium bis(trifluoromethanesulfonyl)imide, n-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyridinium bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium bis(trifluoromethanesulfonyl)imide, methyltrioctylammonium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-allylimidazolium bis(trifluoromethanesulfonyl)imide, 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, and the like, as well as their derivatives, modifications, and combinations.

[0065] When utilized, a portion of the carrier medium or solvent can be added separately, jointly with a mixture of components (A), (C), and / or (D), or as a whole with the reaction mixture to the chlorosilane compound (A), catalyst (C), and / or olefin compound (D) (i.e., when utilized), or otherwise combined with the chlorosilane compound (A), catalyst (C), and / or olefin compound (D). The total amount of carrier medium / solvent present in the reaction mixture will be selected by those skilled in the art, for example, based on the specific components (A), (C), and / or (D) selected, the reaction parameters employed, etc.

[0066] In some embodiments, the reaction is carried out at elevated temperatures. The elevated temperature will be selected and controlled based on the specific chlorosilane compound (A), catalyst (C), and / or olefin compound (D) selected, the reaction vessel used (e.g., whether open to ambient pressure, sealed, sealed under positive pressure (e.g., positive pressure of ethylene (B))), the presence and boiling point of the carrier medium, etc. Also, since the temperature of the reaction can affect the pressure in the vessel and thus the concentration of dissolved ethylene therein, the temperature can be selected based on the type of silylation desired (i.e., based on the specific organosilicon compound prepared). Thus, given the selected reaction conditions and parameters and the description herein, those skilled in the art will readily select an elevated temperature.

[0067] Generally, the elevated temperature is greater than ambient temperature to 300 °C, such as 30 °C to 250 °C, alternatively 40 °C to 200 °C. In certain embodiments, the elevated temperature is greater than ambient temperature to 200 °C, such as 30 °C to 150 °C, alternatively 40 °C to 150 °C, alternatively 40 °C to 125 °C, alternatively 40 °C to 100 °C, alternatively 50 °C to 100 °C. In some such embodiments, the silylation reaction is configured as a dehydrogenative coupling reaction. In other embodiments, the elevated temperature is generally greater than ambient temperature to 200 °C, such as 60 °C to 200 °C, alternatively 70 °C to 200 °C, alternatively 70 °C to 150 °C, alternatively 80 °C to 150 °C, alternatively 90 °C to 150 °C, alternatively 100 °C to 150 °C. In certain such embodiments, the silylation reaction is configured as a hydrosilylation reaction.

[0068] As described above, the reaction can be carried out at about ambient pressure or alternatively can be carried out under high pressure (e.g., superatmospheric pressure). For example, in some embodiments, the vessel is pressurized with ethylene (e.g., via a gas manifold) such that the reaction is carried out at a pressure greater than atmospheric pressure. Generally, ethylene is employed at a pressure less than 200,000 kPa, such as 100 to 20,000 kPa. However, the total pressure is not particularly limited as a separate parameter of the reaction conditions but is selected / controlled / achieved based on the relative amount of dissolved ethylene in the reaction, as described above.

[0069] In certain embodiments, the reaction is carried out at atmospheric pressure. In other embodiments, the reaction is carried out at a pressure of about atmospheric pressure to 20,000 kPa, such as 100 kPa to 15,000 kPa, alternatively 100 kPa to 12,000 kPa, alternatively 100 kPa to 11,000 kPa, alternatively 100 kPa to 10,500 kPa. In some embodiments, ethylene is used at a pressure greater than atmospheric pressure to 200,000 kPa, such as 105 kPa to 25,000 kPa, alternatively 150 kPa to 20,000 kPa, alternatively 200 kPa to 20,000 kPa, alternatively 500 kPa to 20,000 kPa, alternatively 1,000 kPa to 20,000 kPa, alternatively 2,000 kPa to 20,000 kPa, alternatively 5,000 kPa to 20,000 kPa.

[0070] It should be understood that the high temperature and / or high pressure can also be different from the above ranges, especially when both high temperature and high pressure are utilized. In particular, as described above, the pressure of the reaction affects the reaction selectivity and may be affected by the reaction temperature employed, as described above. In a specific embodiment, the high temperature and pressure are jointly selected to provide supercritical conditions with respect to one or both of components (A) and (B). Similarly, it should also be understood that the reaction parameters can be modified during the reaction of component (A) with component (B). For example, the temperature, pressure, and other parameters can be independently selected or modified during the reaction. Any one of these parameters can independently be an ambient parameter (e.g., room temperature and / or atmospheric pressure) and / or a non-ambient parameter (e.g., low temperature or high temperature and / or low pressure or high pressure). Any parameter can also be modified dynamically, modified in real time, i.e., during the process, or any parameter can be invariant (e.g., during the duration of the reaction, or any part thereof).

[0071] In a specific embodiment, the reaction is carried out at a pressure greater than ambient pressure to 200,000 kPa, such as greater than 101.3 kPa to 20,000 kPa, alternatively 110 kPa to 10,000 kPa, alternatively 150 kPa to 5,000 kPa, alternatively 200 kPa to 2,000 kPa, alternatively 200 kPa to 1,000 kPa, alternatively 250 kPa to 1,000 kPa, alternatively 250 kPa to 750 kPa. In some such embodiments, the silylation reaction is configured as a dehydrogenative coupling reaction.

[0072] The time for reacting components (A) and (B) to prepare a silicone compound varies with scale, reaction parameters and conditions, choice of specific components, etc. At relatively large scales (e.g., greater than 1 kg, alternatively 5 kg, alternatively 10 kg, alternatively 50 kg, alternatively 100 kg), the reaction can proceed for several hours, such as 2 hours to 48 hours, alternatively 3 hours to 36 hours, alternatively 4 hours to 24 hours, alternatively for 6 hours, 12 hours, 18 hours, 24 hours, 36 hours or 48 hours, as can be readily determined by one of ordinary skill in the art (e.g., by monitoring the conversion of the chlorosilane compound (A), the production of the silicone compound, etc., via chromatographic methods and / or spectroscopic methods). In certain embodiments, after components (A) and (B) are combined in the presence of catalyst (C), optionally after reaching a high temperature and / or high pressure, the reaction proceeds for a time greater than 0 hours to 48 hours, such as 1 hour to 36 hours, alternatively 1 hour to 24 hours, alternatively 1 hour to 12 hours, alternatively 2 hours to 12 hours, alternatively 2 hours to 10 hours.

[0073] Generally, the reaction of components (A) and (B) prepares a reaction product comprising a silicone compound. Specifically, during the reaction, the reaction mixture comprising components (A) and (B) contains a large amount of the silicone compound and small amounts of components (A) and (B). Once the reaction is complete (e.g., one of components (A) and (B) is consumed and no additional silicone compound is prepared, etc.), the reaction mixture can be referred to as the reaction product comprising the silicone compound. Thus, the reaction product generally contains any remaining amounts of components (A), (B), (C) and optional (D), as well as their degradation products and / or other reaction products (e.g., by-products and / or other materials), any carrier medium or solvent used, etc.

[0074] In certain embodiments, the method further comprises separating and / or purifying the organosilicon compound from the reaction product. As used herein, separating an organosilicon compound is generally defined as increasing the relative concentration of the organosilicon compound compared to other compounds with which it is combined (e.g., in the reaction product or its purified form). Thus, as understood in the art, separation / purification can include removing other compounds from such a combination (i.e., reducing the amount of impurities / other components combined with the organosilicon compound, e.g., in the reaction product) and / or removing the organosilicon compound itself from the combination. Any suitable separation technique and / or protocol can be employed. Examples of suitable separation techniques include distillation, stripping / evaporation, extraction, filtration, washing, partitioning, phase separation, chromatography, etc. As will be understood by those skilled in the art, any one of these techniques can be used in combination (i.e., sequentially) with any other technique to separate the organosilicon compound. It should be understood that separation can include and thus can be referred to as purifying the organosilicon compound. However, purifying the organosilicon compound can include alternative and / or additional techniques compared to those used for separating the organosilicon compound. Regardless of the specific technique chosen, the separation and / or purification of the organosilicon compound can be carried out sequentially (i.e., in order) with the reaction itself and can thus be automated. In other cases, purification can be a separate procedure to which the reaction product containing the organosilicon compound is subjected. In certain embodiments, the organosilicon compound is purified by venting and / or purging the reaction vessel and the reaction product, e.g., to remove any remaining ethylene (B), hydrogen (H2), etc. prepared during the reaction. In some such embodiments, the reaction product is cooled during venting and / or purging.

[0075] In a specific embodiment, the preparation method includes separating the organosilicon compound from the reaction product by distillation, wherein the organosilicon compound is removed from one or more components of the reaction product that are distillates (e.g., catalyst (C)). The distillation is generally carried out at subatmospheric pressure and temperature (i.e., low temperature and reduced pressure). The reduced pressure and low temperature will be selected by those skilled in the art based on the selected reaction conditions and parameters, the components used, the organosilicon compound prepared, etc. The reduced pressure is generally operated as a vacuum, although any reduced pressure between vacuum and atmospheric pressure (i.e., 101.325 kPa) can be used. For example, the reduced pressure can be greater than 0 to 50, alternatively greater than 0 to 40, alternatively greater than 0 to 30, alternatively greater than 0 to 20, alternatively greater than 0 to 10, alternatively greater than 0 to 5, alternatively greater than 0 to 4, alternatively greater than 0 to 3, alternatively greater than 0 to 2 kPa (e.g., measured in mmHg).

[0076] Typically, the reaction product prepared by the reaction of components (A) and (B) includes catalyst residues containing a ruthenium complex. The ruthenium complex of the catalyst residues can be the same as the Ru(0) complex used or used as component (C) in the reaction, or alternatively, substantially the same as the Ru(0) complex. Alternatively, the ruthenium complex of the catalyst residues can be a derivative of the Ru(0) complex used or used as component (C) in the reaction, for example, formed from the Ru(0) complex during the reaction.

[0077] In certain embodiments, the preparation method includes separating the catalyst residues from the reaction mixture using, for example, one or more of the above techniques. In some embodiments, the organosilicon compound is separated from the reaction product by distillation, and the catalyst residues are separated by removing other components of the reaction product as distillates therefrom.

[0078] As described above, the separated catalyst residues can be used to catalyze, optionally in the presence of component (D), another silylation reaction of components (A) and (B), for example. Thus, in certain embodiments, the preparation method includes using the catalyst residues (i.e., recycling catalyst (C)) to catalyze a further silylation reaction, which can be the same as or different from the initial reaction used to prepare the catalyst residues. For example, in some embodiments, the method includes two consecutive dehydrogenative coupling reactions using catalyst (C) and the catalyst residues. In other embodiments, the method includes two consecutive hydrosilylation reactions using catalyst (C) and the catalyst residues, respectively. However, the preparation method provides increased process utility by allowing the temporary alteration of the reaction selectivity (e.g., by varying the ethylene partial pressure within the reaction vessel) to vary the process output (e.g., depending on the organosilicon compound prepared). Thus, in certain embodiments, the method includes performing the silylation reaction described above, separating catalyst (C) (or its derivative, e.g., by collecting the catalyst residues), and then using the separated catalyst (C) or its derivative to catalyze an additional silylation reaction different from the first reaction. For example, in some such embodiments, the silylation reaction is further defined as dehydrogenative coupling, and the additional silylation reaction is further defined as hydrosilylation. In other such embodiments, the silylation reaction is further defined as hydrosilylation, and the additional silylation reaction is further defined as dehydrogenative coupling.

[0079] It should be understood that for any number of serially independent selected silylation reactions, catalyst (C) can be recycled in this manner any number of times, and the reactions can each be the same as or different from any other silylation reaction. In certain embodiments, catalyst (C) is recycled at least once, alternatively at least twice, alternatively at least 3, 4, 5, 6, 7, 8, 9, or 10 times.

[0080] As described above, the preparation method prepares organosilicon compounds. As will be understood by those skilled in the art, the particular organosilicon compound prepared varies with the particular chlorosilane compound (A) used in the preparation method and the type of silylation reaction selected. More specifically, as understood from the above description of the structures of components (A) and (B) and their reaction parameters, the method prepares the organosilicon compound as a dehydrogenative coupling product or a hydrosilylation product of the chlorosilane compound (A) and ethylene (B). In either case, the chlorosilane compound (A) forms the organochlorosilane backbone of the organosilicon compound, and ethylene (B) forms a vinyl group or an ethyl group bonded to the silicon atom of the organochlorosilane backbone.

[0081] Generally, the organosilicon compound has the general formula Y-SiCl x R 3-x , where Y is a vinyl group or an ethyl group, and the subscript x and each R are as defined above. More specifically, the subscript x is typically 1, 2, or 3, and each R is an independently selected unsubstituted hydrocarbon group having 1 to 18 carbon atoms (e.g., methyl, ethyl, etc.).

[0082] In some embodiments, Y is a vinyl group and x is 1 or 2, such that the organosilicon compound can be further defined as an organovinylchlorosilane compound. For example, in some embodiments, when the chlorosilane compound (A) is further defined as a diorganochlorosilane (e.g., where the subscript x is 1 such that the compound (A) has the formula HSiClR2), the preparation method prepares the organosilicon compound as a diorganovinylchlorosilane compound having the formula (H2CCH)SiClR2, where each R is as defined above. In other embodiments, when the chlorosilane compound (A) is further defined as an organodichlorosilane (e.g., where the subscript x is 2 such that the compound (A) has the formula HSiCl2R), the preparation method prepares the organosilicon compound as an organovinyldichlorosilane compound having the formula (H2CCH)SiCl2R, where R is as defined above. In some embodiments, each R is an alkyl group, such that the organosilicon compound is further defined as a dialkylvinylchlorosilane or an alkylvinyldichlorosilane. In certain embodiments, each R is methyl (i.e., CH3), such that the organosilicon compound is further defined as a dimethylvinylchlorosilane or a methylvinyldichlorosilane.

[0083] In certain embodiments, Y is an ethyl group and x is 1 or 2, such that the organosilicon compound can be further defined as an organoethylchlorosilane compound. For example, in some embodiments, when the hydro-chlorosilane compound (A) is further defined as a diorganohydrochlorosilane (e.g., where the subscript x is 1 such that the compound (A) has the formula HSiClR2), the preparation method prepares the organosilicon compound as a diorganoethylchlorosilane compound having the formula (H3CCH2)SiClR2, where each R is as defined above. In other embodiments, when the hydro-chlorosilane compound (A) is further defined as an organodihydrochlorosilane (e.g., where the subscript x is 2 such that the compound (A) has the formula HSiCl2R), the preparation method prepares the organosilicon compound as an organoethyldichlorosilane compound having the formula (H3CCH2)SiCl2R, where R is as defined above. In some embodiments, each R is an alkyl group, such that the organosilicon compound is further defined as a dialkylethylchlorosilane or an alkylethyldichlorosilane. In certain embodiments, each R is a methyl group (i.e., CH3), such that the organosilicon compound is further defined as a dimethylethylchlorosilane or a methylethyldichlorosilane. It should be understood that the organosilicon compound can also include combinations of such compounds, i.e., when more than one hydro-chlorosilane compound (A) is utilized in the preparation method.

[0084] The organosilicon compounds prepared according to the preparation method can be used in a variety of end-use applications, such as as discrete components in compositions, including curable compositions, personal care or cosmetic compositions, etc. For example, when the prepared organosilicon compound contains at least one aliphatic unsaturated group per molecule (e.g., a silicon-bonded vinyl group prepared from ethylene (B)), the organosilicon compound can be used in further olefin-based reactions, such as for hydrosilylation reactions. For example, the organosilicon compound can be a component in a hydrosilylation-curable composition. When the prepared organosilicon compound contains at least one ethyl group per molecule (e.g., a silicon-bonded ethyl group prepared from ethylene (B)), the organosilicon compound can be used as a capping agent or a structural block to reduce the terminal methyl content of silicone compositions.

[0085] The following examples are intended to illustrate the embodiments described herein and should not be construed in any way as limiting the scope of the invention.

[0086] Characterization program

[0087] Gas chromatography (GC)

[0088] Gas chromatography (GC) data was obtained using an Agilent 7890A gas chromatograph equipped with a Thermo Scientific TG-5HT column. Detection of the eluted substances was accomplished using a flame ionization detector (FID). The sample (1 μL) was injected onto the column, and the column was held at 40 °C for 8 minutes from the injection time, after which the temperature was increased to 300 °C at a rate of 15 °C / min. The elution times were determined by injecting standards, and the product quantification was determined by integrating the areas of the elution signals. Exemplary standards (with elution times) include dimethylchlorosilane (1.90 minutes), methyldichlorosilane (1.93 minutes), vinyldimethylchlorosilane (2.44 minutes), vinylmethyldichlorosilane (2.79 minutes), ethyldimethylchlorosilane (2.62 minutes), and ethylmethyldichlorosilane (3.05 minutes).

[0089] Components and materials

[0090] Certain components utilized in the examples are listed in Table 1 below.

[0091] Table 1: Components and materials used

[0092] Compound Description Hydrosilane (A-1) Dimethylchlorosilane Hydrosilane (A-2) Methyldichlorosilane Catalyst (C-1) <![CDATA[Ru3(CO) 12 > Olefin (D-1) Norbornene Ligand (L-1) Triphenylphosphine Ligand (L-2) Pentafluorophenyldiphenylphosphine Ligand (L-3) Tris(3,5-bis(trifluoromethyl)phenyl)phosphine Ligand (L-4) Tricyclohexylphosphine Ligand (L-5) 1,3-Bis(dicyclohexylphosphino)propane Ligand (L-6) Triphenyl phosphite Ligand (L-7) 1,3-Bis(diphenylphosphino)propane Solvent (S-1) Toluene

[0093] Examples 1-2: Preparation of vinyldimethylchlorosilane (ClSi(CH3)2(CHCH2))

[0094] The catalyst (C) (1.9 mg, 9.0 μmol Ru) was added to a Schlenk tube under ambient conditions. The tube was then evacuated and backfilled with nitrogen several times. Then the solvent (S-1) (12 mL) was transferred to the tube via cannula, and the resulting mixture was stirred for twenty minutes under gentle heating to form a solution. The solution was then cooled to room temperature and the hydrosilane (A) (100 μL, 900 μmol) was charged, and the resulting solution was transferred via cannula to a Fischer-Porter tube equipped with a stir bar and a manifold for introducing ethylene. The tube was then pressurized with ethylene to five bar and then vented. The tube was pressurized with ethylene, followed by venting, an additional four times to substantially eliminate nitrogen from the tube. The tube was then pressurized with ethylene to five bar, and the solution was heated to 100 °C and held at that temperature for two hours with stirring. The solution was then cooled to -78 °C and the tube was vented. The solution was then transferred via cannula to a Schlenk tube and then to a distillation apparatus with a collection vessel cooled to -78 °C. The solution was then distilled under subatmospheric pressure and at a temperature below 25 °C to remove the volatile product mixture containing the organosilicon compound as the distillate from the catalyst residue. The distillate was then warmed to room temperature and analyzed by gas chromatography to evaluate the conversion of the hydrosilane (A) and the yield of the organosilicon compound, the results of which are listed in Table 2 below.

[0095] Comparative Example 1

[0096] The procedures shown in Examples 1-2 above were repeated without adding catalyst (C), and the results are listed in Table 2 below.

[0097] Table 2 - Parameters and characteristics of Examples 1 to 2 and Comparative Example 1

[0098] Examples: Comparative Example Example 1 Example 1 Example 2 Hydrosilane (A): A-1 A-1 A-1 Catalyst (C): None C-1 C-1 Conversion of A (%) N / A >99 >99 Yield (%) N / A 75 79

[0099] In Examples 1-2, the organosilicon compound prepared was vinyldimethylchlorosilane. As shown in Table 2, the exemplary method provided near-complete conversion of the hydrosilane starting material with good yields of dehydrogenative coupling products. In each of Examples 1-2, ethyldimethylchlorosilane was identified as the major byproduct, thus demonstrating hydrosilylation as a competing reaction under the conditions utilized. Also as shown in Table 2 above, significant conversion of hydrosilane (A-1) was observed in the absence of catalyst (C) (see Comparative Example 1).

[0100] Examples 3-11: Preparation of vinyldimethylchlorosilane (ClSi(CH3)2(CHCH2))

[0101] Catalyst (C-1) (1.9 mg, 9.0 μmol Ru) and ligand (L) were added to a Schlenk tube under ambient conditions. The tube was then evacuated and backfilled with nitrogen several times. Then, solvent (S) (12 mL) was transferred into the tube through a cannula, and the resulting mixture was stirred for twenty minutes under gentle heating to form a solution. The solution was then cooled to room temperature and charged with hydrosilane (A-1) (100 μL, 900 μmol), and the resulting mixture was transferred through a cannula into a Fischer-Porter tube equipped with a stir bar and a manifold for introducing ethylene. The tube was then pressurized with ethylene to five bar and then vented. The tube was pressurized with ethylene, followed by venting, an additional four times to substantially eliminate nitrogen from the tube. The tube was then pressurized with ethylene to five bar, and the solution was heated to 100 °C and maintained at this temperature with stirring for two hours. The solution was then cooled to -78 °C, and the tube was vented. The solution was then transferred through a cannula into a Schlenk tube and then into a distillation apparatus with a collection vessel cooled to -78 °C. The solution was then distilled under subatmospheric pressure and at a temperature below 25 °C to remove the volatile product mixture containing the organosilicon compound as the distillate from the catalyst residue. The distillate was then warmed to room temperature and analyzed by gas chromatography to evaluate the conversion of hydrosilane (A-1) and the yield of the organosilicon compound. The specific parameters and evaluation results for Examples 3-11 are listed in Table 3 below.

[0102] Table 3: Parameters and characteristics of Examples 3-11

[0103] Example Ligand (L) Amount of L (mg [μmol]): Conversion of (A) (%) Yield (%) Example 3 L-1 4.7

[18] >99 88 Example 4 L-1 4.7

[18] >99 84 Example 5 L-2 6.3

[18] >99 91 Example 6 L-2 6.3

[18] >99 91 Example 8 L-3 4.0

[18] >99 82 Example 9 L-4 1.7

[18] >99 75 Example 7 L-5 3.9[9.0] >99 80 Example 10 L-6 1.9[9.0] >99 78 Example 11 L-7 1.2[9.0] >99 77

[0104] In Examples 3 - 11, the organosilicon compound prepared was vinyldimethylchlorosilane. As shown in Table 3 above, the exemplary method provided near - complete conversion of the hydrosilane starting material, with good yields of dehydrogenative coupling products. In each of Examples 3 - 11, ethyldimethylchlorosilane was identified as the major by - product, thus demonstrating hydrosilylation as a competing reaction under the conditions utilized.

[0105] Examples 12-14: Preparation of vinyldimethylchlorosilane (ClSi(CH3)2(CHCH2))

[0106] Under ambient conditions, the catalyst (C - 1) (1.9 mg, 9.0 μmol) and ligand (L) were added to a Schlenk tube. The tube was then evacuated and backfilled with nitrogen several times. Then the solvent (S - 1) (12 mL) was transferred into the tube via a cannula, and the resulting mixture was stirred for twenty minutes under gentle heating to form a solution. The solution was then cooled to room temperature and charged with hydrosilane (A - 1) (100 μL, 900 μmol) and Sacrificial olefin (D - 1), and the resulting mixture was transferred via a cannula to a Fischer - Porter tube equipped with a stir bar and a manifold for introducing ethylene. The tube was then pressurized with ethylene to five bar, and then vented. The tube was pressurized with ethylene and then vented, an additional four times, to substantially eliminate nitrogen from the tube. Then the tube was pressurized with ethylene to five bar, and the solution was heated to 100 °C and held at this temperature with stirring for two hours. The solution was then cooled to - 78 °C, and the tube was vented. Then the solution was transferred via a cannula to a Schlenk tube, and then to a distillation apparatus with a collection vessel cooled to - 78 °C. The solution was then distilled under sub - atmospheric pressure and at a temperature below 25 °C to remove the volatile product mixture containing the organosilicon compound as the distillate from the catalyst residue. The distillate was then warmed to room temperature and analyzed by gas chromatography to evaluate the conversion of hydrosilane (A - 1) and the yield of the organosilicon compound. The specific parameters and evaluation results for Examples 12 - 14 are listed in Table 4 below.

[0107] Table 4: Parameters and characteristics of Examples 12-14

[0108] Examples: Example 12 Example 13 Example 14 Olefin (D-1) (mg [mmol]): 420[4.5] 420[4.5] 420[4.5] Ligand (L-1) (mg [μmol]): None 4.7

[18] None Ligand (L-2) (mg [μmol]): None None 6.3

[18] Conversion of (A) (%) >99 >99 >99 Yield (%) 84 88 96

[0109] In Examples 12-14, the organosilicon compound prepared was vinyldimethylchlorosilane. As shown in Table 4 above, the exemplary method provided near-complete conversion of the hydrosilane starting material, with good yields of the dehydrogenative coupling product. In each of Examples 12-14, ethyldimethylchlorosilane was identified as the major by-product, thus demonstrating hydrosilylation as a competing reaction under the conditions utilized.

[0110] Examples 15-20: Preparation of vinylmethyldichlorosilane (Cl2MeSiCHCH2)

[0111] Under ambient conditions, the catalyst (C-1) (2.1 mg, 9.6 μmol) and ligand (L) were added to a Schlenk tube. The tube was then evacuated and backfilled with nitrogen several times. Then the solvent (S) (12 mL) was transferred into the tube via cannula, and the resulting mixture was stirred for twenty minutes under gentle heating to form a solution. The solution was then cooled to room temperature and charged with hydrosilane (A-2) (100 μL, 900 μmol), and the resulting mixture was transferred via cannula to a Fischer-Porter tube equipped with a stir bar and a manifold for introducing ethylene. The tube was then pressurized with ethylene to five bar, and then vented. The tube was pressurized with ethylene, followed by venting, an additional four times to substantially eliminate nitrogen from the tube. Then the tube was pressurized with ethylene to five bar, and the solution was heated to 100 °C and held at this temperature for a certain time (T) with stirring. The solution was then cooled to -78 °C, and the tube was vented. The solution was then transferred via cannula to a Schlenk tube, and then to a distillation apparatus having a collection vessel cooled to -78 °C. The solution was then distilled under sub-atmospheric pressure and at a temperature below 25 °C to remove the volatile product mixture containing the organosilicon compound as the distillate from the catalyst residue. The distillate was then warmed to room temperature and analyzed by gas chromatography to evaluate the conversion of hydrosilane (A-2) and the yield of the organosilicon compound. The specific parameters and evaluation results for Examples 15-20 are listed in Table 5 below.

[0112] Comparative Example 2

[0113] The procedure shown in Examples 15-20 above was repeated without the addition of catalyst (C), and the results are listed in Table 5 below.

[0114] Table 5: Parameters and characteristics of Examples 15-20 and Comparative Example 2

[0115]

[0116] In Examples 15 - 20, the organosilicon compound prepared was dichloromethylvinylsilane. As shown in Table 5 above, the exemplary method converted the hydrosilane starting material to the dehydrogenative coupling product in sufficient yield. A significant conversion of hydrosilane (A - 2) was observed in the absence of catalyst (C) (see Comparative Example 2). In each of Examples 15 - 20, ethylmethyldichlorosilane was identified as the major by - product, thus demonstrating hydrosilylation as a competing reaction under the conditions utilized.

[0117] Examples 21-22: Preparation of vinyldimethylchlorosilane (ClSi(CH3)2(CHCH2))

[0118] Example 21: First preparation

[0119] The hydrosilane was dehydrogenatively coupled with ethylene using a catalyst in a first preparation to obtain an organosilicon compound (Example 21). Specifically, catalyst (C - 1) (1.9 mg, 9.0 μmol) was added to a Schlenk tube under ambient conditions. The tube was then evacuated and backfilled with nitrogen several times. Then, solvent (S - 1) (12 mL) was transferred into the tube via a cannula, and the resulting mixture was stirred for twenty minutes under gentle heating to form a solution. The solution was then cooled to room temperature and charged with hydrosilane (A - 1) (100 μL, 900 μmol), and the resulting solution was transferred via a cannula to a Fischer - Porter tube equipped with a stir bar and a manifold for introducing ethylene. The tube was then pressurized with ethylene to five bar and then vented. The tube was pressurized with ethylene and then vented, an additional four times, to substantially eliminate nitrogen from the tube. The tube was then pressurized with ethylene to five bar, and the solution was heated to 100 °C and held at that temperature with stirring for two hours. The solution was then cooled to - 78 °C, and the tube was vented. The solution was then transferred via a cannula to a Schlenk tube and then to a distillation apparatus with a collection vessel cooled to - 78 °C. The solution was then distilled at sub - atmospheric pressure and at a temperature below 25 °C to a volume of approximately 2 mL, removing a first product mixture containing the organosilicon compound as the distillate and leaving a concentrated catalyst residue, which was set aside. The distillate was then warmed to room temperature and analyzed by gas chromatography with the following results: conversion of dimethylchlorosilane > 99%; yield of vinyldimethylchlorosilane = 75%; ethyl - dimethylchlorosilane as the major by - product.

[0120] Example 22: Second preparation

[0121] The hydrosilane is dehydrogenatively coupled with ethylene using a recycled catalyst in a second preparation to obtain an organosilicon compound (Example 22). In particular, the concentrated catalyst residue additionally placed in Example 21 above was transferred to a Schlenk tube and diluted to 12 mL with a solvent (S-1). The resulting mixture was then used in the procedure of Example 21 above to obtain a second product mixture containing the organosilicon compound, and the second product mixture was analyzed by gas chromatography to evaluate the conversion of the hydrosilane (A-1) and the yield of the organosilicon compound from the second preparation, with the following results: conversion of dimethylchlorosilane > 99%; yield of vinyldimethylchlorosilane = 76%; ethyldimethylchlorosilane as the main by-product.

[0122] Examples 23-32: Preparation of vinyldimethylchlorosilane (ClSi(CH3)2(CHCH2))

[0123] Example 23: First preparation

[0124] The hydrosilane is dehydrogenatively coupled with ethylene using a catalyst in a first preparation to obtain an organosilicon compound (Example 23). In particular, the catalyst (C-1) (1.9 mg, 9.0 μmol) and the ligand (L-2) (6.3 mg, 18 μmol) were added to a Schlenk tube under ambient conditions. The tube was then evacuated and backfilled with nitrogen several times. Then, the solvent (S-1) (12 mL) was transferred to the tube through a cannula, and the resulting mixture was stirred for twenty minutes under gentle heating to form a solution. The solution was then cooled to room temperature and charged with the hydrosilane (A-1) (100 μL, 900 μmol), and the resulting solution was transferred to a Fischer-Porter tube equipped with a stir bar and a manifold for introducing ethylene through a cannula. The tube was then pressurized with ethylene to five bar and then vented. The tube was pressurized with ethylene and then vented, an additional four times, to substantially eliminate the nitrogen from the tube. The tube was then pressurized with ethylene to five bar, and the solution was heated to 100 °C and held at that temperature with stirring for two hours. The solution was then cooled to -78 °C, and the tube was vented. The solution was then transferred to a Schlenk tube through a cannula and then to a distillation apparatus with a collection vessel cooled to -78 °C. The solution was then distilled under subatmospheric pressure and at a temperature below 25 °C to a volume of approximately 2 mL, removing the first product mixture containing the organosilicon compound as the distillate, and leaving behind the concentrated catalyst residue, which was put aside. The distillate was then warmed to room temperature and analyzed by gas chromatography, and the results are shown in Table 6 below.

[0125] Example 24: Second preparation

[0126] Transfer the separately placed concentrated catalyst residue in Example 23 to a Schlenk tube and dilute it to 12 mL with solvent (S-1). Then, in a second preparation, use the resulting mixture in the procedure of Example 23 to obtain a second product mixture (Example 24) containing a silicone compound and a second concentrated catalyst residue. Then, heat the second product mixture to room temperature and analyze it by gas chromatography. The results are shown in Table 6 below.

[0127] Examples 25-32: Third preparation

[0128] Using the concentrated catalyst residue prepared in the previous preparation (i.e., starting from the second concentrated catalyst residue prepared in Example 24), sequentially repeat the procedure of Example 25 above to obtain eight product mixtures (Examples 25 - 32) containing silicone compounds. The product mixtures of Examples 25 - 32 are each analyzed by gas chromatography. The results are shown in Table 6 below.

[0129] Table 6: Continuous preparation of vinyldimethylchlorosilane in Examples 23-32

[0130] Example Conversion of (A) (%) Yield (%) Example 23 >99 81 Example 24 >99 86 Example 25 >99 88 Example 26 >99 89 Example 27 >99 89 Example 28 >99 86 Example 29 >99 87 Example 30 >99 80 Example 31 >99 80 Example 32 >99 74

[0131] In Examples 23 - 32, the silicone compound prepared is vinyldimethylchlorosilane, and ethyldimethylchlorosilane is identified as the main by-product in each preparation. As shown in Table 6 above, the exemplary methods and materials provide an almost complete conversion of the hydrosilane starting material with good yields of dehydrogenative coupling products. In addition, the reaction products are easily removed from the catalyst residue, which can be conveniently recycled in a continuous preparation without additional processing steps or loss of conversion or yield.

[0132] Examples 33-34: Selective preparation of vinyl-functionalized silane and ethyl-functionalized silane

[0133] Example 33: Preparation of vinyldimethylchlorosilane (ClSi(CH3)2(CHCH2))

[0134] In an inert glove box, measure solvent (S-1) (30.15 g) into a glass screw-top container. Then, charge catalyst (C-1) (26 mg) and a magnetic stir bar into the container, seal it, and place it on a magnetic stir plate outside the glove box. Stir and heat the mixture to 50 °C to dissolve the catalyst metal complex, and then return it to the glove box and allow it to cool to ambient temperature. Then, add hydrosilane (A-1) (13.54 g) to the solution to obtain a reaction mixture, and then add nonane (1.13 g) as an internal reference standard for gas chromatography analysis. Charge a reference sample (1 g aliquot) of the reaction mixture into a glass vial, dilute it with solvent (S-1) (4 g), and analyze it to determine the starting concentration of hydrosilane (A-1) in the reaction mixture.

[0135] Transfer the reaction mixture to a stainless-steel sample cylinder, seal it, remove it from the glove box, and connect it to an inert reactor system (100 mL stirred reactor, Parr Inst. Co.) via a stainless-steel transfer line. Then purge with nitrogen for 10 minutes. Transfer the reaction mixture to the reactor by nitrogen pressurization (10 psig, approximately 68.9 kPa), and purge the reactor with ethylene (3 x 100 psig, approximately 689 kPa; stir for 1 min). Then pressurize the reactor with ethylene (610 psig, approximately 4,206 kPa) and stir (350 rpm) until saturated (stable pressure), seal it, and heat it to 40 °C with stirring and hold at this temperature. After a 10-minute stabilization period, then heat the reactor to 100 °C (ramp at 2 °C / min to prevent temperature overshoot) and hold at this temperature for 90 minutes. Then cool the reactor to room temperature (external fan), depressurize, and then purge three times with nitrogen (100 psig, approximately 689 kPa). Then connect the reactor to a nitrogen stream (10 psig, approximately 68.9 kPa) which is used to transfer the reaction mixture to a stainless-steel sample cylinder. Seal the cylinder and transport it to an inert glove box, and transfer the contents to a glass vial. Load a reference sample (1 g aliquot) of the reaction mixture into a glass vial, dilute it with solvent (S-1) (4 g), and analyze by gas chromatography to evaluate the conversion of hydrosilane (A-1) and the yield of organosilicon compounds, with the following results: yield of vinyldimethylchlorosilane = 84%; ethyl dimethylchlorosilane as the main by-product (13.5%).

[0136] Example 33: Preparation of Ethyldimethylchlorosilane (ClSi(CH3)2(CH2CH3))

[0137] In an inert glove box, measure solvent (S-1) (30.15 g) into a glass screw-top container. Then charge the container with catalyst (C-1) (25 mg) and a magnetic stir bar, seal it, and place it on a magnetic stir plate outside the glove box. Stir and heat the mixture to 50 °C to dissolve the catalyst metal complex, and then return it to the glove box and allow it to cool to ambient temperature. Then add hydrosilane (A-1) (13.50 g) to the solution to obtain a reaction mixture, and then add nonane (1.18 g) as an internal reference standard for gas chromatography analysis.

[0138] A reference sample (1 g aliquot) of the reaction mixture was charged into a glass vial, diluted with solvent (S-1) (4 g), and analyzed to determine the starting concentration of hydrosilane (A-1). The reaction mixture was transferred to a stainless steel sample cylinder, which was then sealed, removed from the glove box, and connected to an inert reactor system (100 mL stirred reactor, Parr Inst. Co.) via a stainless steel transfer line, and then purged with nitrogen for 10 minutes. The reaction mixture was transferred to the reactor by nitrogen pressurization (10 psig, ca. 68.9 kPa), and the reactor was purged with ethylene (3 x 100 psig, ca. 689 kPa; 1 min stirring). The reactor was then pressurized with ethylene (200 psig, ca. 1,379 kPa) and stirred (450 rpm) until saturated (steady pressure), sealed, and heated to 40 °C with stirring (350 rpm) and held at this temperature. After a 10-minute stabilization period, the reactor was heated to 100 °C (ramped at 2 °C / min to prevent temperature overshoot) and held at this temperature for 140 minutes. The reactor was then cooled to room temperature (external fan), depressurized, and then purged three times with nitrogen (100 psig, ca. 689 kPa). The reactor was then connected to a nitrogen stream (10 psig, ca. 68.9 kPa), which was used to transfer the reaction mixture to a stainless steel sample cylinder. The cylinder was sealed and transported to an inert glove box, and the contents were transferred to a glass vial. A reference sample (1 g aliquot) of the reaction mixture was charged into a glass vial, diluted with solvent (S-1) (4 g), and analyzed by gas chromatography to evaluate the conversion of hydrosilane (A-1) and the yield of organosilicon compounds, with the following results: conversion of dimethylchlorosilane = 73% (23% of the starting dimethylchlorosilane remained unreacted); yield of ethyldimethylchlorosilane = 64%; vinyl dimethylchlorosilane as the major byproduct (13%).

[0139] The foregoing description relates to general and specific embodiments of the present disclosure. However, various changes and modifications may be made without departing from the spirit and broader aspects of the present disclosure as defined in the appended claims, which are to be interpreted in accordance with the principles of patent law, including the doctrine of equivalents. Accordingly, the present disclosure is presented for illustrative purposes and should not be construed as an exhaustive description of all embodiments of the present disclosure or as limiting the scope of the claims to the specific elements illustrated or described in connection with these embodiments. For example, any reference to an element in the singular using the articles "a / an", "the", or "said" should not be construed as limiting the element to the singular. Additionally, it should be understood that the terms "right angle", "orthogonal", "perpendicular", and "parallel" are generally employed herein in a relative rather than an absolute sense. Further, it should be understood that the terms "substantially", "about", "approximately", etc. indicate minor deviations from the characteristic being modified. Such deviations may be 0 - 10% of the particular characteristic, alternatively 0 - 5%, alternatively 0 - 3%.

Claims

1. A method for preparing an organosilicon compound, the method comprising: By subjecting (A) a hydrosilane compound and (B) ethylene to hydrosilylation in the presence of a catalyst comprising (C) a Ru3(CO) 12 complex and a phosphorus ligand having the formula R 1 2PR 2 or an organic phosphite ligand having the formula (R 1 O)2P(OR 2 ), the organosilicon compound is prepared by carrying out the reaction, wherein each R 1 is an unsubstituted aryl group, aralkyl group or cycloalkyl group, or haloaryl group, independently selected, and R 2 is R 1 or an alkaryl group.

2. The method according to claim 1, wherein the method further comprises preparing the catalyst (C).

3. The method according to claim 1 or 2, wherein (i) the phosphorus ligand has a Tolman electronic parameter of 2,060 to 2,090 cm -1 ; (ii) the phosphorus ligand has a Tolman cone angle of 115 to 185°; or (iii) any combination of (i)-(ii).

4. The method according to claim 1 or 2, wherein the hydrosilylation is further defined as the dehydrogenative coupling of the chlorosilane compound (A) and the ethylene (B) such that the organosilicon compound is prepared as a vinylchlorosilane compound, and wherein the dehydrogenative coupling is carried out at a stoichiometric ratio of the chlorosilane compound (A) to ethylene (B) of at least 1:2 (A):(B).

5. The method according to claim 4, wherein the organic phosphite ligand comprises an unsubstituted triaryl phosphite.

6. The method according to claim 4, wherein the dehydrogenative coupling of components (A) and (B) is carried out in the presence of an olefin compound (D) having an unsaturated aliphatic group, wherein the olefin compound includes norbornene.

7. The method according to claim 1 or 2, wherein the hydrosilylation is further defined as the hydrosilylation of the chlorosilane compound (A) and the ethylene (B) such that the organosilicon compound is prepared as an ethylchlorosilane compound, and wherein the hydrosilylation is carried out at a stoichiometric ratio of the chlorosilane compound (A) to ethylene (B) of less than 1:2 (A):(B).

8. The method according to any one of claims 1 or 2, wherein the organosilicon compound is prepared in a reaction product, and wherein the method further comprises: (I) separating the catalyst (C) from the reaction product; and (II) using the separated catalyst (C) to catalyze a further hydrosilylation reaction.

9. The method according to any one of claims 1 or 2, wherein the hydrosilylation is carried out under the following conditions: (i) at a high temperature of 60 °C to 200 °C; (ii) at a pressure of atmospheric pressure to 110 bar; (iii) in the presence of a solvent, (iv) based on the total amount of component (A) utilized, the concentration of the catalyst (C) is from 0.0001% by weight to 5% by weight; or (v) any combination of (i) to (iv).

10. The method according to any one of claims 1 or 2, the method having: (i) a conversion of at least 85% of the chlorosilane compound (A); (ii) a yield of at least 75% of the organosilicon compound; or (iii) both (i) and (ii).

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