Selective preparation of vinyl- and ethyl-functionalized chlorosilanes.

Abstract

A method for preparing organosilicon compounds via the selective silylation of ethylene is disclosed. The method comprises reacting (A) a hydridochlorosilane compound and (B) ethylene in the presence of a catalyst (C) via silylation, thereby preparing the organosilicon compound. The silylation can be selectively carried out as a dehydrogenative coupling reaction to prepare the organosilicon compound as a vinylchlorosilane compound, or as a hydrosilylation reaction to prepare the organosilicon compound as an ethylchlorosilane compound. The catalyst (C) comprises a Ru(0) complex and can be recycled for use in subsequent silylation reactions without purification. Organosilicon compounds prepared by this method are also disclosed.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to and the entire benefit of U.S. Provisional Patent Application No. 62 / 949,883, filed December 18, 2019, and U.S. Provisional Patent Application No. 63 / 059,909, filed July 31, 2020, the contents of which are incorporated herein by reference.

[0002] FIELD OF THEINVENTION The present disclosure relates generally to methods for preparing organosilicon compounds, and more specifically, to methods for selectively preparing vinylchlorosilanes and ethylchlorosilanes via tunable silylation. [Background technology]

[0003] Hydrosilylation reactions are generally known in the art and involve an addition reaction between silicon-bonded hydrogen and aliphatic unsaturation. Hydrosilylation reactions are utilized in a variety of applications, such as crosslinking components of curable compositions. Hydrosilylation reactions can also be utilized to prepare separate components or compounds, such as components for inclusion in such curable compositions. Typically, hydrosilylation reactions are carried out in the presence of platinum metal-based catalysts due to their superior catalytic activity and stability. Platinum metals are generally much more expensive than other metals with lower catalytic activity, while non-platinum catalysts have instability when exposed to ambient conditions. In particular, non-platinum catalysts are prone to undesirable side reactions with ambient oxygen and water, which can limit their use and potential end uses.

[0004] Similar to hydrosilylation, dehydrogenative silylation reactions are also known in the art and similarly involve the reaction between silicon-bonded hydrogen and aliphatic unsaturation. However, in dehydrogenative silylation, there is no addition reaction; instead, aliphatic unsaturation is vinylically bonded to silicon, and hydrogen gas (H2) is produced as a by-product. Thus, dehydrogenative silylation reactions can be used to prepare unsaturated compounds (e.g., olefin-functional compounds), which can then undergo additional functionalization and / or coupling reactions (e.g., via hydrosilylation).

[0005] Unfortunately, catalysts for dehydrogenative silylation reactions suffer from many of the same drawbacks associated with hydrosilylation catalysts, such as sensitivity to oxygen, water, and even light. Moreover, while such drawbacks have been overcome by recent advances in hydrosilylation catalysts, many catalyst 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 addition reactions, especially for the least substituted olefins, thus resulting in nonselective reactions and low yields with undesirable product mixtures. Furthermore, many conventional dehydrogenative silylation conditions are not functional group tolerant, thus limiting their use. Summary of the Invention

[0006] The present disclosure provides a method for preparing an organosilicon compound. The method includes reacting (A) a hydridochlorosilane compound and (B) ethylene via silylation in the presence of (C) a catalyst comprising a Ru(0) complex, thereby preparing the organosilicon compound. The hydridochlorosilane compound (A) is represented by the general formula HSiCl x R 3-x where subscript x is 1, 2, or 3, and each R is an independently selected unsubstituted hydrocarbyl group having 1 to 18 carbon atoms. Silylation may be selectively used as a dehydrocoupling or hydrosilylation reaction, and may have the formula (HCCH)SiCl x R 3-xor as a vinyl chlorosilane compound having the formula (CH3CH2)SiCl x R 3-x

[0033] The organosilicon compounds can be prepared as ethylchlorosilane compounds having the formula: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] A method for preparing organosilicon compounds ("the preparation method") is provided herein. As will be understood from the description herein, the preparation method includes a controllable ethylene silylation to selectively prepare organosilicon compounds having one or more ethylene-derived vinyl or ethyl groups. Silylation is achieved by the use of a stored catalyst under adjustable conditions, which selectively promotes dehydrocoupling or hydrosilylation reactions to give organosilicon compounds having the desired ethylene-derived functionality. The specific materials and conditions used also allow the catalyst to be recovered and recycled for use in 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.

[0008] As will be understood by those skilled in the art, the vinyl or ethyl functionality provided by silylation, as well as any other functional groups compatible with the conditions of the preparation method, provide organosilicon compounds with many uses in a myriad of compositions and methods, including preparing curable compositions (such as those based on one or more silicones) and their various components.For example, in the case of vinyl functionality, the organosilicon compounds can be utilized, for example, as starting materials, reagents, building blocks, functionalizing compounds, etc., to prepare and / or crosslink curable compositions.In the case of ethyl functionality, such as endblocking or capping agents, the organosilicon compounds can be utilized for different purposes in similar compositions and materials, or for unique purposes, such as preparing low molecular weight silicones with reduced methyl content.

[0009] The preparation method includes reacting (A) a hydridochlorosilane compound and (B) ethylene in the presence of (C) a catalyst comprising a Ru(0) complex. The hydridochlorosilane compound (A), ethylene (B), and Ru(0) complex-containing catalyst (C) are described in order below, along with additional components that may be utilized in the preparation method, which may be referred to collectively as "components" of the preparation method (i.e., "component (A)", "component (B)", "component (C)", etc., respectively), or similarly as "starting materials", "compounds", and / or "reagents" (A), (B), and / or (C), etc.

[0010] As will be understood by those skilled in the art from the description herein, the preparation method prepares an organosilicon compound through the silylation of components (A) and (B) as catalyzed by a catalyst (C), i.e., by forming silicon-bonded vinyl or ethyl groups in place of silicon-bonded hydrogen atoms of the hydridochlorosilane compound (A) ("reaction"). In this regard, as used herein, the term "silylation" should be understood to encompass both dehydrogenation and hydrosilylation coupling reactions, regardless of any specific reaction mechanism. In an exemplary embodiment, as described below, the components and conditions of the silylation reaction used in the preparation method are preserved across both reaction types, so that general references to reactions, components, conditions, etc. are understood to be applicable to the entire preparation method. However, since the preparation method provides for the selection of either of the two silylation mechanisms introduced above, the term "dehydrogenation coupling" is used herein in reference to the preparation of a vinyl-functional organosilicon compound through the dehydrogenation silylation of ethylene (B) with the hydridochlorosilane compound (A). Similarly, the term "hydrosilylation" is used herein to refer to the preparation of an ethyl-functional organosilicon compound by hydrosilylation of ethylene (B) with a hydridochlorosilane compound (A).

[0011] As introduced above, component (A) is a hydridochlorosilane compound, i.e., an organosilicon compound having at least one silicon-bonded hydrogen atom (i.e., a Si-H group) and at least one silicon-bonded chlorine atom (i.e., a Si-Cl group). The hydridochlorosilane compound (A) is not otherwise particularly limited.

[0012] Typically, component (A) has the general formula HSiCl x R 3-x where subscript x is 1, 2, or 3, and each R is an independently selected hydrocarbyl group. In some embodiments, the hydridochlorosilane compound (A) is further defined as an organohydridochlorosilane, whereby the subscript x in the above general formula is 1 or 2. For example, in some such embodiments, the subscript x is 1, whereby the hydridochlorosilane compound (A) is further defined as a diorganohydridochlorosilane, whereby the hydridochlorosilane compound (A) is further defined as a diorganohydridochlorosilane, whereby the hydridochlorosilane compound (A) is further defined as a diorganohydridochlorosilane, whereby the hydridochlorosilane compound (A) is further defined as a diorganohydridochlorosilane, whereby the hydridochlorosilane compound (A) is further defined as a diorganohydridodi ...

[0013] With respect to the organohydridochlorosilanes of the above formula for use as component (A), each R is an independently selected hydrocarbyl group. Suitable hydrocarbyl groups may be substituted or unsubstituted. With respect to such hydrocarbyl groups, the term "substituted" refers to a hydrocarbon moiety in which one or more hydrogen atoms are replaced with atoms other than hydrogen (e.g., halogen atoms such as chlorine, fluorine, bromine, etc.), a carbon atom in the hydrocarbon chain is replaced with an atom other than carbon (i.e., R may include one or more heteroatoms (oxygen, sulfur, nitrogen, etc.) in the carbon chain), or both. It will thus be understood that R can include or be a hydrocarbon moiety having one or more substituents in and / or on its carbon chain / backbone (i.e., attached to and / or integral to its carbon chain / backbone), such that R can include or be an ether, ester, etc.

[0014] Generally, suitable hydrocarbyl groups for R may be independently linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups include aryl groups, and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may be independently monocyclic or polycyclic. Linear and branched hydrocarbyl groups may be independently saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. General examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, and the like, as well as derivatives, variants, and combinations thereof. 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 branched saturated hydrocarbon groups, for example, 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 will be understood that in certain embodiments, such alkenyl groups may participate in the silylation reaction chemistry. Thus, in certain embodiments, R is free or substantially free of alkene-containing functional groups. Examples of suitable monovalent halogenated hydrocarbon groups (i.e., halocarbon groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include the alkyl groups described above, in which one or more hydrogen atoms are replaced with halogen atoms, such as F or Cl.Specific examples of halogenated alkyl 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, and derivatives thereof. Examples of halogenated aryl groups include the above-mentioned aryl groups, in which one or more hydrogen atoms are replaced with halogen atoms such as F or Cl. Specific examples of halogenated aryl 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 linear or unbranched unsubstituted hydrocarbyl groups. In certain embodiments, each R is independently selected from unsubstituted hydrocarbyl groups having 1 to 18 carbon atoms.

[0015] When the subscript x is 1, thereby further defining the hydridochlorosilane compound (A) as a diorganohydridochlorosilane, each R may be the same as or different from the other R in the hydridochlorosilane compound (A). In certain embodiments, each R is the same as the other R in the hydridochlorosilane compound (A). In other embodiments, one R is different from the other R in the hydridochlorosilane 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 groups, ethyl groups, and the like. In certain embodiments, each R is methyl. For example, in some such embodiments, the hydridochlorosilane compound (A) has the formula HSiCl x(CH3) 3-x where subscript x is as defined above. In certain such embodiments, component (A) comprises dimethylchlorosilane (i.e., of formula HSiCl(CH3)2), methyldichlorosilane (i.e., of formula HSiCl2(CH3)), or a combination thereof.

[0016] Component (B) comprises or is ethylene. Ethylene is not particularly limited and may be used in neat form (i.e., free or substantially free of other components / compounds). In other words, component (B) may consist of ethylene, may consist essentially of ethylene, or may include ethylene in combination with other components. For example, in some embodiments, the method includes introducing a reactor fluid that comprises, consists essentially of, or consists of ethylene to a vessel or reactor that contains at least components (A) and (C). In such embodiments, the reactor fluid may include components other than ethylene, such as a carrier vehicle, which is or includes a material that is typically inert (i.e., does not react with components (A), (B), or (C)) under the reaction conditions utilized in the preparation method, as will be understood by those skilled in the art. Examples of such carrier vehicles include inert gases such as nitrogen (g) (N2), helium (g) (He), argon (g) (Ar), and combinations thereof. ). However, in certain embodiments, component (B) is utilized in neat form and consists essentially of ethylene (ie, substantially free or free of carrier vehicle).

[0017] Ethylene may be utilized in gaseous form in or as component (B). It will thus be appreciated that in certain embodiments, the preparation process is carried out in a vessel containing an ethylene atmosphere, as described in more detail below.

[0018] The preparation method can utilize any amount of components (A) and (B), and more specifically, can include hydridochlorosilane compound (A) and ethylene (B) in various amounts or ratios depending on the desired properties of the reaction, the specific organosilicon compound to be prepared, and / or the properties of the starting materials used. As will be understood by those skilled in the art, components (A) and (B) are each monofunctional with respect to the silylation reaction, respectively, so 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 (A):(B) of 1:1 (i.e., a stoichiometric ratio of component (A) to component (B) of 1:1). Thus, ethylene is typically utilized in a molar amount at least equal to the molar amount of component (A) utilized. For example, components (A) and (B) can be utilized in a molar ratio of (A):(B) of 1:1. As will be appreciated from the discussion below, an excess of ethylene (e.g., a slight excess, a moderate excess, or a large excess) can also be utilized. Generally, components (A) and (B) are utilized in a molar ratio of (A):(B) of 1:≧1, such as from 1:1 to 1:100 (A):(B).

[0019] As mentioned above, the silylation reaction of the preparation method can be adjusted to select dehydrogenative coupling or hydrosilylation, thereby preparing organosilicon compounds with vinyl or ethyl functional groups derived from ethylene, respectively (i.e., "reaction selectivity"). More specifically, the reaction selectivity can be controlled through the ratio of reactable ethylene to hydridochlorosilane compound (A) in the reaction, i.e., the ratio of the amount of ethylene in solution (i.e., solubilized ethylene) to the amount (e.g., concentration) of hydridochlorosilane compound (A) in solution. As will be understood by those skilled in the art, the concentration of ethylene in the liquid / reactive phase of the reaction can be determined by direct measurement (e.g., by analytical techniques such as Raman spectroscopy, gas chromatography (GC)) or theoretical estimation (e.g., based on gas-liquid equilibrium calculation), or any other technique known in the art.

[0020] Generally, the preparation method includes reacting components (A) and (B) in a stoichiometric ratio of (A):(B) of at least 1:2 to prepare vinyl-functional organosilicon compounds via dehydrogenative coupling, or reacting components (A) and (B) in a stoichiometric ratio of (A):(B) of less than 1:2 to prepare ethyl-functional organosilicon compounds via hydrosilylation. In other words, all components and other reaction parameters are the same, silylation can be adjusted by changing the relative amount of ethylene available to react with the hydridochlorosilane compound (A), dehydrogenative coupling is favored at a relative ratio (B):(A) of 2 or more (i.e., (B):(A) of ≧2:1), and hydrosilylation is favored at a relative ratio (B):(A) of less than 2 (i.e., (B):(A) of <2:1).

[0021] For example, in some embodiments, silylation is further defined as the dehydrogenative coupling of a hydridochlorosilane 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 with a stoichiometric ratio of hydridochlorosilane compound (A) to ethylene (B) of at least 1:2, alternatively at least 1:3 (A):(B). For example, in certain embodiments, ethylene is utilized in an amount sufficient to provide a molar ratio of ethylene (B) to hydridochlorosilane compound (A) of (B):(A) of 2:1 to 100:1, for example, 2:1 to 50:1, alternatively 2:1 to 25:1, alternatively 2:1 to 20:1, alternatively 2:1 to 15:1, alternatively 2:1 to 10:1, alternatively 2:1 to 6:1, alternatively 3:1 to 6:1. It will be appreciated that ratios outside these ranges may also be utilized.

[0022] Typically, the specific amount of components (A) and (B) reacting through dehydrogenation coupling is 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 dehydrogenation coupling reaction with at least 75% conversion of hydridochlorosilane compound (A) to vinylchlorosilane compound, such as at least 80%, alternatively at least 85%, alternatively at least 90%, alternatively at least 95%, alternatively at least 98% conversion.In some such embodiments, the dehydrogenation coupling reaction also includes at least 75% yield of organosilicon compound (e.g., vinylchlorosilane compound), such as at least 80%, alternatively at least 85%, alternatively at least 90%, alternatively at least 95% yield.

[0023] In certain embodiments, the silylation is further defined as the hydrosilylation of a hydridochlorosilane 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 hydridochlorosilane compound (A) to ethylene (B) of less than 1:2 (A):(B). For example, in certain embodiments, ethylene is utilized in an amount sufficient to provide a molar ratio of ethylene (B) to hydridochlorosilane compound (A) of (B):(A) of 1:1 to less than 2:1, such as greater than 1:1 to less than 2:1, or greater than 1:1 to 1.9:1 (B):(A). Higher or lower ratios may also be utilized, depending, for example, on the selected reaction components and parameters, the desired selectivity / yield of the reaction, and the like.

[0024] Typically, the specific amount of components (A) and (B) reacting through hydrosilylation is 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 with at least 75% conversion of hydridochlorosilane compound (A) to ethylchlorosilane compound, such as at least 80%, alternatively at least 85%, alternatively at least 90%, alternatively at least 95%, alternatively at least 98% conversion.In some such embodiments, the hydrosilylation reaction also includes at least 75% yield of organosilicon compound (e.g., ethylchlorosilane compound), such as at least 80%, alternatively at least 85%, alternatively at least 90%, alternatively at least 95% yield.

[0025] Typically, the specific amount of components (A) and (B) is 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 dehydrogenation coupling reaction with at least 75% conversion of hydridochlorosilane compound (A) to vinylchlorosilane compound, such as at least 80%, alternatively at least 85%, alternatively at least 90%, alternatively at least 95%, alternatively at least 98% conversion.In some such embodiments, the dehydrogenation coupling reaction also includes at least 50% yield of organosilicon compound (e.g., vinylchlorosilane compound), such as at least 60%, alternatively at least 65%, alternatively at least 70%, alternatively at least 75% yield.

[0026] As introduced above, component (C) is a catalyst, more specifically, a catalyst containing 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 may be any Ru(0) complex capable of catalyzing the silylation of ethylene with the hydridochlorosilane compound (A).

[0027] 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(η 4 -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 and the like, as well as derivatives, modifications, and combinations thereof. Those skilled in the art will appreciate that the ligands represented by COD and COT are cyclooctadiene and cyclooctatriene, respectively. The ligands represented by the general formula PR'3 are tertiary phosphorus compounds (e.g., phosphines, phosphites, etc.), where each R' is an independently selected substituted or unsubstituted aryl, aralkyl, or cycloalkyl group, or their corresponding alkoxy or aryloxy groups, as exemplified by those described herein.

[0028] In certain embodiments, the Ru(0) complex comprises a triruthenium complex or a derivative thereof. An example of a triruthenium complex is {[Ru(bda)-(pic)2(μ-O)]2Ru(pic)2(H2O)2} 2+ , {[Ru3(μ-H)(μ-η 3 -dpa-C,N,N)(CO)}, {(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 derivatives, modifications, and combinations thereof. One of ordinary skill in the art will appreciate that the ligands represented by bda, pic, dpa, acac, dmbpy, and HAT are 2,2-bipyridine-6,6-dicarboxylate, 2-picolylamine, dipicolylamine, acetylacetonate, 4,4'-dimethyl-2,2'-bipyridine, and 1,4,5,8,9,12-hexaazatriphenylene, or deprotonated forms thereof, or deprotonated forms thereof, respectively.

[0029] As will be understood from the exemplary complexes above and the further description and examples below, Ru(0) complexes can include phosphorus ligands. Examples of phosphorus ligands include phosphines, phosphites, phosphates, phosphine oxides, phosphoramidites, phosphonium salts, phosphinoamines, chlorophosphines, phosphinoimines, phosphorodiamidites, phosphinites, phosphonates, phosphonites, triaminophosphines, trisilylphosphines, and the like, as well as derivatives, modifications, and combinations thereof. Those skilled in the art will understand that such ligands can be utilized in ionic form (e.g., from protonation / deprotonation), which is encompassed in the examples above and shown in various embodiments herein. Specific examples of phosphorus ligands include phosphine, trimethylphosphine, triphenylphosphine, methyldiphenylphosphine, trifluorophosphine, trimethylphosphite, triphenylphosphite, 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), tri(orthotolyl)phosphine, (2,4,6-triisopropylphenyl)dicyclopentylphosphine, and the like, as well as derivatives, modifications, and combinations thereof. Those skilled in the art will appreciate that such phosphorus ligands include phosphite versions of the above phosphines, as well as homo- and hetero-substituted phosphines and phosphites having any one or more of the phosphorus binding groups exemplified herein.

[0030] In certain embodiments, the Ru(0) complex of the catalyst (C) has the general formula R 1 3P, wherein each R 1 are independently selected hydrocarbon groups. Examples of suitable hydrocarbon groups include the hydrocarbyl groups described above for R. As will be appreciated by one of ordinary skill in the art, each R 1can be independently selected based on factors such as steric hindrance, electronics (e.g., electron donating, electron conducting, or electron withdrawing effects), or the like, or a combination thereof. 1 may be selected to impart chirality or to impart symmetry to the catalyst. In these or other embodiments, R 1 may be independently selected to effect reactive regioselectivity, such as reverse Markovnikov selectivity (e.g., 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, t-butyl, other branched alkyls, aryls, alkaryls, aralkyls, substituted aryls (such as pentafluorophenyl, etc.), and the like. In certain embodiments, each R 1 are the same. In some embodiments, the phosphorus ligand has the formula R 1 2PR 2 wherein 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 multidentate ligand having two or more phosphorus atoms. Specific examples of such phosphorus ligands include 1,3-bis(dicyclohexylphosphino)propane and 1,3-bis(diphenylphosphino)propane. In certain embodiments, 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, aralkyl, or cycloalkyl group; R 2 is R 1 or alkaryl groups. Examples of such organophosphine ligands include substituted and unsubstituted triarylphosphines, tricycloalkylphosphines, bis(diarylphosphino)alkanes, bis(dicycloalkylphosphino)alkanes, and combinations thereof.

[0031] In certain embodiments, the Ru(0) complex of the catalyst (C) has the formula 1 O)2P(OR 2 ) wherein R 1 and R 2 is as defined above. In some such embodiments, each R 1 and R 2 contains a substituted or unsubstituted aryl group, such that the organophosphite ligand is further defined as a triarylphosphite ligand.

[0032] Additional examples of suitable phosphorus ligands include those with intermediate Tollman electronic parameters (TEP) and / or intermediate Tollman cone angles (TCA). For example, in some embodiments, the Ru(0) complex of catalyst (C) has a TEP of 2,050-2,100 cm. -1 TEP, for example, 2,060-2,090 or 2,065-2,085 cm -1 In these or other embodiments, the Ru(0) complex includes a phosphorus ligand having a TCA of 100-200°, e.g., 115-185°, or alternatively, 130-170°. As will be appreciated by those skilled in the art, the TEP of a phosphorus ligand is based on the A1 symmetric CO stretching frequency (ω) of a standard nickel tricarbonyl complex including the ligand (i.e., of formula (R'3P)Ni(CO)3, where the ligand PR'3 is a phosphorus ligand and is as defined above) and can be determined by measuring a vibrational spectrum (i.e., infrared (IR) or Raman) of the complex according to the following relationship: TEP = ω(CO,Ni;A1) = 2056.1 + pL, where pL is the ligand specific increment for the CO stretching frequency (ω). Typically, using P(tBu)3 as the standard, ω(CO,A1) = 2056.1 cm -1pL(P(tBu)3) is set to 0 so that: As will be appreciated by those skilled in the art, the TCA of a phosphorus ligand in a transition metal complex is the solid angle formed by the metal at the apex and the outermost edge / perimeter of a cone minimally sized around the van der Waals sphere of the ligand atom, and may be determined using computational space-filling models and / or empirical bond characterization. Methods and materials for such determination of TEP and / or TCA are described in more detail in Tolman, Chemical Reviews, 1977, vol 77(3) pp313-348, the characterization methods and phosphorus ligands of which are incorporated herein by reference.

[0033] The particular phosphorus ligand utilized in the Ru(0) complex of catalyst (C) can be selected based on the particular hydridochlorosilane compound (A) utilized and / or the particular organosilicon compound being prepared. For example, in certain embodiments, the reaction components / parameters are selected to prepare a vinyl-functional organosilicon compound (e.g., via dehydrogenative coupling of components (A) and (B), where the hydridochlorosilane compound (A) is an organohydridochlorosilane and the Ru(0) complex of catalyst (C) comprises a phosphorus ligand. In some such embodiments, the hydridochlorosilane compound (A) is a diorganohydridochlorosilane having the formula HSiClR2 and the Ru(0) complex of catalyst (C) comprises an organophosphine ligand. In other such embodiments, the hydridochlorosilane compound (A) is an organohydridodichlorosilane having the formula HSiCl2R and the Ru(0) complex of catalyst (C) comprises an organophosphite ligand.

[0034] In certain embodiments, the Ru(0) complex is triruthenium dodecacarbonyl (i.e., the formula Ru(CO) 12or a derivative thereof, or is triruthenium dodecacarbonyl or a derivative thereof. In some such embodiments, the triruthenium dodecacarbonyl derivatives are further defined as ligand-exchanged derivatives of triruthenium dodecacarbonyl having one or more phosphorus ligands. In certain embodiments, the one or more phosphorus ligands are selected from phosphines and phosphites, such as any of those described herein. It is understood that such ligand-exchanged derivatives may also be prepared from ruthenium compounds / complexes other than triruthenium dodecacarbonyl, and are included within the scope of the Ru(0) complexes herein, regardless of whether they are prepared from triruthenium dodecacarbonyl or another ruthenium compound / complex, or obtained by other means.

[0035] The Ru(0) complex may include other ligands than those mentioned above, such as those containing and / or derived from amines, ketones, diones, olefins, nitriles, carbenes, etc., and combinations thereof. The additional ligands may be prepared in situ (i.e., during the preparation process), such as via solvent exchange and / or normal catalytic workup of the Ru(0) complex in the presence of components (A) and (B), as will be appreciated from the further discussion below regarding the catalyst residue and its isolation / recycling / reuse.

[0036] The Ru(0) complex of catalyst (C) may be utilized in any form, such as neat (i.e., free of solvent, carrier vehicle, diluent, etc.) or processed in a carrier vehicle, such as a solvent or dispersant (e.g., any of those listed and / or described herein), which are independently selected by one of skill in the art (e.g., taking into consideration the particular component (A) selected, the solubility of the Ru(0) complex, etc.). Thus, catalyst (C) may consist of or consist essentially of the Ru(0) complex, or may include additional components, such as a carrier vehicle, a diluent, etc.

[0037] Catalyst (C) may be utilized in any amount selected by those skilled in the art, which may be based, for example, on the specific catalyst (C) selected (e.g., the concentration / amount of its active Ru species), the nature / type of component (A) selected, the reaction parameters employed, the scale of the reaction (e.g., the total amount of component (A) utilized, etc.). The molar ratio of catalyst (C) to components (A) and / or (B) utilized in the reaction may affect the rate and / or amount of silylation to prepare organosilicon compounds. Thus, the amount of catalyst (C) compared to components (A) and / or (B), as well as the molar ratio therebetween, may vary. Typically, these relative amounts and molar ratios are selected to maximize the concentration of components (A) and (B) while minimizing the loading amount of catalyst (C) (e.g., to improve the economic efficiency of the reaction, improve the ease of purification of the reaction product formed, etc.).

[0038] In certain embodiments, catalyst (C) is utilized in the reaction in an amount of 0.000001 to 50 weight percent (i.e., weight / weight), based on the total amount of component (A) utilized. For example, catalyst (C) may be used in an amount of 0.000001 to 25, alternatively 0.00001 to 10, alternatively 0.0001 to 5 weight percent, based on the total amount of component (A) utilized. In some embodiments, catalyst (C) is utilized in an amount sufficient to provide a ratio of Ru(0) complex to hydridochlorosilane compound (A) of (C):(A) of 1:10 to 1:1,000,000, alternatively 1:50 to 1:1,000, alternatively 1:100 to 1:500. Such ratios may be weight ratios (i.e., weight / weight of (C):(A), or active components thereof), or molar ratios of (C):(A), or active components thereof. It will be understood that amounts and ratios outside the above ranges may be utilized as well. For example, catalyst (C) may be utilized in a stoichiometric amount (i.e., the catalytic amount described above) based, for example, on the total amount of component (B) (i.e., the ethylene) utilized in the preparation process.

[0039] It will be appreciated that catalyst (C) may comprise a combination of various Ru(0) complexes, such as 2, 3, 4, 5 or more Ru(0) complexes that may be the same or different (e.g., in terms of ligand identity, shape, ruthenium content, etc.) from any other Ru(0) complex of catalyst (C).

[0040] 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 exemplary Ru(0) complexes are known in the art, using compounds commercially available from a variety of sources. Thus, catalyst (C) can be prepared prior to the reaction of components (A) and (B) or in situ (i.e., during the reaction of components (A) and (B), for example, by combining the components of catalyst (C) with components (A) and / or (B)).

[0041] In certain embodiments, catalyst (C) is prepared as part of a preparation method, i.e., the preparation method includes preparing catalyst (C). Preparing catalyst (C) may include preparing a Ru(0) complex or providing a Ru(0) complex in a form suitable for use in catalyzing the silylation of components (A) and (B).

[0042] In certain embodiments, the preparation method includes preparing a Ru(0) complex to obtain catalyst (C). In such embodiments, preparing a Ru(0) complex typically includes combining a catalyst precursor compound and a ligand precursor compound, optionally in the presence of a support vehicle, to obtain a Ru(0) complex (e.g., via ligand exchange), which can be used directly in the reaction of components (A) and (B) (e.g., used directly as catalyst (C)) or can be purified, treated, combined with a support vehicle, or otherwise modified to prepare catalyst (C). However, it will be understood that preparing a Ru(0) complex can include any number of additional steps / processes / procedures not described in further detail below, such as oxidizing or reducing ruthenium complexes / compounds with different oxidation states to obtain a Ru(0) complex.

[0043] Examples of catalyst precursor compounds generally include Ru(0) and triruthenium complexes, including those described above, as well as derivatives, modifications, and combinations thereof. For example, in certain embodiments, the catalyst precursor compound is triruthenium dodecacarbonyl. Examples of ligand precursor compounds include the phosphorus ligands described above, including protonated and / or salt forms thereof. For example, in certain embodiments, the ligand precursor compound is a tertiary phosphorus compound. In some such embodiments, the tertiary phosphorus compound is represented by the formula R 1 2PR 2 wherein R 1 and R 2 is as defined above. In other such embodiments, the tertiary phosphorus compound has the formula (R 1 O)2P(OR 2 ), wherein R 1 and R 2 is as defined above.

[0044] The catalyst and ligand precursor compounds may be provided, prepared, or otherwise obtained (e.g., from a commercial source). In certain embodiments, preparing the catalyst (C) further comprises preparing the catalyst and / or ligand precursor compound prior to and / or in combination with complexing the ruthenium of the catalyst precursor compound with a ligand precursor compound to obtain a Ru(0) complex. As understood in the art, the catalyst and ligand precursor compounds may be prepared or synthesized via a number of routes or techniques.

[0045] As introduced above, the Ru(0) complex may be prepared in a carrier vehicle, such as any of those described herein. For example, the Ru(0) complex may be prepared in a vehicle in which the catalyst (C) is placed during its 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-, m-, and / or p-xylene), mesitylene (i.e., 1,3,5-trimethylbenzene), or the like, or a combination thereof. Depending on various selections, when the catalyst (C) is placed in a vehicle or solvent, the vehicle or solvent, or a portion thereof, may complex with Ru(0) and become, for example, a ligand or other component of the Ru(0) complex.

[0046] In certain embodiments, preparing catalyst (C) includes combining the catalyst and ligand precursor compound in the presence of an aromatic solvent, thereby preparing a Ru(0) complex in the aromatic solvent. Typically, the catalyst and ligand precursor compound and the aromatic solvent are combined in a vessel or reactor to prepare the Ru(0) complex and / or catalyst (C). The vessel or reactor may be heated or cooled in any suitable manner, for example, via a jacket, mantle, exchanger, bath, coil, etc. For example, in some embodiments, the catalyst and ligand precursor compound may be combined in an aromatic solvent at an elevated temperature to obtain a Ru(0) complex, thus preparing catalyst (C). The elevated temperature for preparing catalyst (C) is selected and controlled depending on the particular catalyst and / or ligand precursor compound selected, the particular aromatic solvent and / or other carrier vehicle utilized, the reaction vessel selected (e.g., open to ambient pressure, closed, under reduced pressure, etc.), and the like. Thus, the elevated temperature for preparing catalyst (C) will be selected by one of skill in the art in view of the selected reaction conditions and parameters, and the description herein. The elevated temperature for preparing catalyst (C) is typically from above ambient temperature to 300° C., for example, from 50 to 250° C., alternatively from 60 to 200° C., alternatively from 70 to 175° C., alternatively from 75 to 150° C., alternatively from 80 to 125° C. Higher temperatures outside these ranges can also be used.

[0047] In certain embodiments, the preparation method comprises reacting components (A) and (B) in the presence of (D) an olefinic compound. As will be understood by those skilled in the art, the olefinic compound (D) is typically used in embodiments where the reaction components / parameters are selected to prepare a vinyl-functional organosilicon compound (e.g., via dehydrogenative coupling of components (A) and (B)). The olefinic compound (D) comprises an unsaturated aliphatic hydrocarbon group, which may be referred to as aliphatically unsaturated, ethylenically unsaturated, etc., depending on the particular form of the hydrocarbon group having unsaturation (e.g., C-C double and / or triple bonds), but is otherwise not particularly limited.

[0048] Generally, olefinic compound (D) contains at least one aliphatically unsaturated group per molecule. However, in certain embodiments, olefinic compound (D) contains at least two aliphatically unsaturated groups per molecule on average. Of course, olefinic compound (D) can also contain any number of additional aliphatically unsaturated groups. Each aliphatically unsaturated group of olefinic compound (D) can be, for example, at terminal, pendant, or both positions in olefinic compound (D) depending on its structure.

[0049] In certain embodiments, the olefinic compound (D) comprises or is an organic compound. In other embodiments, the olefinic compound (D) comprises or is a siloxane. In yet other embodiments, the olefinic compound (D) comprises a silicone-organic hybrid or an organosilicon compound. Various embodiments and examples of the olefinic compound (D) are further disclosed below.

[0050] The aliphatically unsaturated groups of the olefinic compound (D) may be alkenyl and / or alkynyl groups. As will be appreciated 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 alkene) 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 may be cyclic or acyclic, branched or unbranched, substituted or unsubstituted, and combinations thereof. Such groups are generally not limited as to size and / or overall structure other than the olefinic portion, and may contain from 2 to 30 carbon atoms, e.g., from 2 to 24 carbon atoms, alternatively from 2 to 20 carbon atoms, alternatively from 2 to 12 carbon atoms, alternatively from 2 to 10 carbon atoms, alternatively from 2 to 6 carbon atoms, and the like. Alkenyl groups are exemplified by vinyl, vinylidine, allyl, propenyl, and hexenyl groups. Suitable alkenyl groups include internal, external, terminal (e.g., alpha-olefinic), polysubstituted (e.g., cis and trans di-, tri-, and quaternary substituted alkenes), and combinations thereof. Examples of particular alkynyl groups include ethynyl, propynyl, and butynyl groups.

[0051] Examples of compounds suitable for use as the olefin compound (D) include alkenyl compounds (e.g., compounds having at least one alkenyl group), such as butenes (e.g., isobutene, cyclobutene, etc.), pentenes (e.g., 4-methyl-1-pentene, 3-methyl-1-pentene, cyclopentene, 2-methylcyclopentene, 4-methylcyclopentene, etc.), hexenes (e.g., cyclohexene, 3,5,5-trimethyl-1-hexene, vinylcyclohexene, etc.), linear alpha olefins (e.g., 1-heptene, olefins (e.g., cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene, etc.), cyclic olefins (e.g., cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene, etc.), cyclic olefins (e.g., cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene, etc.), cyclic olefins (e.g., cyclohex ... norbornene, 4-methylnorbornene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, vinylnorbornene, etc.), polyolefins (e.g., 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1,3-divinylcyclopentane, dicyclo pentadiene, 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 ene-yne ​​compounds (e.g., 1,3-butadiene, 1,5-hexadiyne, 1-hexen-5-yne, etc.), and the like, as well as derivatives, modifications, and combinations thereof. The particular aliphatically unsaturated groups and / or compounds utilized in or as the olefinic compound (D) are typically selected based on hydrogenation and / or silylation rates. For example, in certain embodiments, the olefinic compound (D) is selected to readily undergo hydrogenation but slowly undergo hydrosilylation. In certain embodiments, the olefinic compound (D) comprises, consists essentially of, or is norbornene or a derivative or analog thereof.

[0052] The preparation method can utilize any amount of component (D), and more specifically, can include the olefinic compound in any amount and / or ratio relative to the desired properties of the reaction (e.g., conversion rate, etc.) and / or the properties of the starting materials used. Typically, component (D) is utilized in an amount sufficient to provide the olefinic compound in a stoichiometric ratio of at least 1:1 based on the number of silicon-bonded hydrogen groups (i.e., the number of Si-H groups capable of undergoing dehydrogenative coupling reactions) of component (A) to be vinylized. Thus, as will be understood by those skilled in the art, the amount of component (D) is typically selected based on the amount and type of hydridochlorosilane (A). An excess or large excess of component (D) can be utilized. For example, components (A) and (D) can be utilized in a stoichiometric ratio of (A):(D) of 1:≧1, such as a ratio of (A):(D) of 1:1 to 1:100. In certain embodiments, component (D) is utilized in an amount sufficient to provide a molar ratio of olefin compound to hydridochlorosilane compound (A) of (D):(A) from 1:1 to 100:1, such as from 1:1 to 10:1, alternatively from 2:1 to 10:1, alternatively from 3:1 to 5:1, (D):(A). Higher or lower ratios may also be utilized.

[0053] The components utilized in the preparation method (i.e., hydridochlorosilane compound (A), ethylene (B), catalyst (C), and / or olefin compound (D)) may be provided "as is," i.e., ready for reaction to prepare the organosilicon compound. Alternatively, any one or more, or all of components (A), (B), (C), and / or (D) may be formed prior to or during the reaction (e.g., as described above, when the method includes preparing catalyst (C)). In certain embodiments, the preparation method further includes preparing hydridochlorosilane 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 catalyst (C). In these or other embodiments, the preparation method further includes preparing olefin compound (D).

[0054] Typically, components (A), (B), (C), and optionally (D) are reacted in a vessel or reactor to prepare the organosilicon compound. As described below, when the reaction is carried out at elevated or reduced temperatures, the vessel or reactor may be heated or cooled in any suitable manner, for example, via a jacket, shroud, exchanger, vessel, coil, etc.

[0055] Components (A), (B), (C), and optionally (D) may be fed together or separately to the vessel, or may be placed in the vessel in any order of addition and in any combination. For example, in certain embodiments, components (A), (B), and (D) are added to a vessel containing component (C), e.g., as a pre-made catalyst or as individual components forming catalyst (C) in situ. In certain embodiments, catalyst (C) is prepared in the vessel, and then components (A) and, optionally, (D) are charged to prepare a solution in the vessel, which is then pressurized with component (B). In some embodiments, components (A) and (D) may be first combined before being added to the vessel, or may be added to the vessel sequentially (e.g., (A) followed by (D)). In general, references herein to a "reaction mixture" generally refer to a mixture comprising components (A), (B), (C), and, if optionally utilized, (D), (e.g., as obtained by combining the components as described above).

[0056] The method can further include stirring the reaction mixture. Stirring can, for example, enhance the mixing and contact of components (A), (B), (C), and optionally (D) when combined in the reaction mixture. Such contact can be performed independently, with stirring (e.g., in parallel or sequentially), or without stirring (i.e., independently or instead), using other conditions. Other conditions can be adapted to enhance the contact and thus the reaction (i.e., silylation) of the hydridochlorosilane compound (A) with ethylene (B) to form the organosilicon compound. Other conditions can be effective conditions to enhance the reaction yield or to minimize the amount of certain reaction by-products included in the reaction product along with the organosilicon compound.

[0057] Components (A) and (B) may be reacted in the presence of a carrier vehicle (e.g., a solvent, diluent, fluid, or combination thereof) such that the reaction takes place in a solution, emulsion, suspension, slurry, biphasic mixture, or combination thereof. The particular solvent, carrier, and / or diluent utilized, and the amount of each used, are independently selected by those skilled in the art based on, for example, the particular hydridochlorosilane compound (A), catalyst (C), and / or olefin compound (D) (if utilized), the particular organosilicon compound being prepared, and the like. Typically, the reaction is carried out under homogeneous conditions (e.g., in solution). However, the reaction may be carried out heterogeneously, with one or more components suspended but not dissolved in the carrier vehicle. Typically, ethylene (B) is utilized in gaseous form, e.g., at a pressure selected to prepare a reaction mixture with the desired molar ratio (A):(B) and thus provide the desired reaction chemistry. However, the other components may be used as a homogenous mixture / solution (ie, dissolved and / or disposed in the carrier vehicle prior to forming a reaction mixture therewith).

[0058] In some embodiments, the reaction is carried out in the presence of a carrier vehicle. The carrier vehicle is not particularly limited, and is typically selected based on the specific hydridochlorosilane compound (A), catalyst (C), and / or olefin compound (D) (if utilized), and the specific organosilicon compound to be prepared.For example, in such an embodiment, the carrier vehicle typically includes or is an oil (e.g., organic oil and / or silicone oil), a fluid, a solvent, etc., or a combination thereof.

[0059] In some embodiments, the carrier vehicle comprises or is an organic solvent. Examples of organic solvents include 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 methylene chloride; chloroform; dimethylsulfoxide; dimethylformamide, acetonitrile; tetrahydrofuran, white spirits; mineral spirits; naphtha; n-methylpyrrolidone, and the like, as well as derivatives, modifications, and combinations thereof.

[0060] In some embodiments, the carrier vehicle comprises or is a silicone fluid. The silicone fluid is typically a low viscosity and / or volatile siloxane. In some embodiments, the silicone fluid is a low viscosity organopolysiloxane, a volatile methyl siloxane, a volatile ethyl siloxane, a volatile methylethyl siloxane, or the like, or a combination thereof. Typically, the silicone fluid has a viscosity of 1 to 1,000 mm at 25°C. 2 Examples of suitable silicone fluids include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3, siloxane, pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, as well as polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylyl methicone, hexamethyldisiloxane, heptamethyloctyltrisiloxane, hexyltrimethicone, and the like, as well as derivatives, modifications, and combinations thereof. Further examples of suitable silicone fluids include 5x10 -7 ~1.5x10-6 m 2 Examples of suitable polyorganosiloxanes include polyorganosiloxanes having a suitable vapor pressure, such as 1000 psi / sec.

[0061] In certain embodiments, the carrier vehicle comprises or is an organic fluid, typically comprising organic oils including volatile and / or semi-volatile hydrocarbons, esters, and / or ethers. Common examples of such organic fluids include C6-C 16 Alkanes, C8-C 16 Isoalkanes (e.g., isodecane, isododecane, isohexadecane, etc.), C8 to C 16 Branched esters (e.g., isohexyl neopentanoate, isodecyl neopentanoate, etc.), as well as derivatives, modifications, and combinations thereof. Additional examples of suitable organic fluids include aromatic hydrocarbons, aliphatic hydrocarbons, alkyl halides, aromatic halides, and combinations thereof. Hydrocarbons include isododecane, isohexadecane, Isopar L (C 11 -C 13 ), Isopar H(C 11 -C 12 ), and hydrogenated polydecene.

[0062] Other carrier vehicles may also be used in the composition. For example, in some embodiments, the carrier vehicle comprises or is an ionic liquid. Examples of ionic liquids include combinations of anions and cations. In general, the anions are selected from alkyl sulfate-based anions, tosylates, sulfonates, bis(trifluoromethanesulfonyl)imide anions, bis(fluorosulfonyl)imide anions, hexafluorophosphate anions, tetrafluoroborate anions, etc., and the cations are selected from imidazolium-based cations, pyrrolidinium-based cations, pyridinium-based cations, lithium cations, etc. However, combinations of multiple cations and anions may also be used. Specific examples of ionic liquids include, typically, 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, and methyltrioctylammonium bis(trifluoromethanesulfonyl)imide. 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 derivatives, modifications, and combinations thereof.

[0063] If utilized, a portion of the support vehicle or solvent may be added individually to the hydridochlorosilane compound (A), catalyst (C), and / or olefin compound (D) (if utilized), added collectively to a mixture of components (A), (C), and / or (D), added together to the reaction mixture, or otherwise combined. The total amount of support vehicle / solvent present in the reaction mixture will be selected by one of skill in the art based, for example, on the particular components (A), (C), and / or (D) selected, the reaction parameters employed, and the like.

[0064] In some embodiments, the reaction is carried out at an elevated temperature. The elevated temperature is selected and controlled depending on the particular hydridochlorosilane compound (A), catalyst (C), and / or olefin compound (D) selected, the reaction vessel utilized (e.g., whether open to ambient pressure, sealed, or under positive pressure (e.g., positive pressure of ethylene (B)), the presence and boiling point of a carrier vehicle, etc. Similarly, the temperature of the reaction can affect the pressure within the vessel and thus the concentration of solubilized ethylene therein, so the temperature can be selected based on the type of silylation reaction desired (i.e., based on the particular organosilicon compound being prepared). Thus, the elevated temperature will be readily selected by one of ordinary skill in the art in view of the reaction conditions and parameters selected, as well as the description herein.

[0065] Typically, the elevated temperature is from ambient to 300° C., for example, from 30 to 250° C., alternatively from 40 to 200° C. The elevated temperature is typically from ambient to 200° C., for example, from 30 to 150° C., alternatively from 40 to 150° C., alternatively from 40 to 125° C., alternatively from 40 to 100° C., alternatively from 50 to 100° C. In some such embodiments, the silylation reaction is configured as a dehydrogenative coupling reaction. In other embodiments, the elevated temperature is from ambient to 200° C., for example, from 60 to 200° C., alternatively from 70 to 200° C., alternatively from 70 to 150° C., alternatively from 80 to 150° C., alternatively from 90 to 150° C., alternatively from 100 to 150° C. In certain such embodiments, the silylation reaction is configured as a hydrosilylation reaction.

[0066] As noted above, the reaction may be carried out at about ambient pressure, or alternatively at elevated pressure (e.g., super-atmospheric 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 pressures greater than atmospheric pressure. Typically, ethylene is used at pressures less than 200,000 kPa, such as 100-20,000 kPa. However, the overall pressure is not specifically limited as an individual parameter of the reaction conditions, but rather is selected / controlled / achieved based on the relative amount of solubilized ethylene in the reaction, as noted above.

[0067] 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 to 20,000 kPa, for example, 100 to 15,000, alternatively 100 to 12,000, alternatively 100 to 11,000, alternatively 100 to 10,500 kPa. In certain embodiments, ethylene is used at a pressure greater than atmospheric to 200,000 kPa, for example, 105 to 25,000, alternatively 150 to 20,000, alternatively 200 to 20,000, alternatively 500 to 20,000, alternatively 1,000 to 20,000, alternatively 2,000 to 20,000, alternatively 5,000 to 20,000 kPa.

[0068] It should be understood that the high temperature and / or high pressure may also differ from the ranges stated above, especially when both high temperature and high pressure are utilized. In particular, as noted above, the pressure of the reaction affects the reaction selectivity and may be influenced by the reaction temperature used as described above. In certain embodiments, the high temperature and high pressure are collectively selected to provide supercritical conditions for one or both of components (A) and (B). It should also be understood that the reaction parameters may be modified during the reaction of components (A) and (B). For example, the temperature, pressure, and other parameters may be independently selected or modified during the reaction. Any of these parameters may independently be ambient parameters (e.g., room temperature and / or atmospheric pressure) and / or non-ambient parameters (e.g., low or high temperatures and / or reduced or elevated pressures). Any parameter may also be dynamically modified, changed in real time, i.e., during the process, or static (e.g., for the duration of the reaction or any portion thereof).

[0069] In certain embodiments, the reaction is carried out at a pressure from above ambient pressure to 200,000 kPa, e.g., from above 101.3 to 20,000, alternatively from 110 to 10,000, alternatively from 150 to 5,000, alternatively from 200 to 2,000, alternatively from 200 to 1,000, alternatively from 250 to 1,000, alternatively from 250 to 750 kPa. In some such embodiments, the silylation reaction is configured as a dehydrogenative coupling reaction.

[0070] The time for which the reaction of components (A) and (B) to prepare the organosilicon compound is carried out is a function of scale, reaction parameters and conditions, the selection of the particular components, etc. On a relatively large scale (e.g., greater than 1 kg, alternatively 5 kg, alternatively 10 kg, alternatively 50 kg, alternatively 100 kg), the reaction can be carried out for several hours, e.g., 2 to 48 hours, alternatively 3 to 36 hours, alternatively 4 to 24 hours, alternatively 6, 12, 18, 24, 36, or 48 hours, as easily determined by one skilled in the art (e.g., by monitoring the conversion of the hydridochlorosilane compound (A), the formation of the organosilicon compound, etc., e.g., by chromatography and / or spectroscopy). In certain embodiments, the time for which the reaction is carried out is greater than 0 to 48 hours, e.g., 1 to 36 hours, alternatively 1 to 24 hours, alternatively 1 to 12 hours, alternatively 2 to 12 hours, alternatively 2 to 10 hours, after components (A) and (B) are combined in the presence of catalyst (C), and optionally after reaching elevated temperature and / or pressure.

[0071] Generally, the reaction of components (A) and (B) prepares a reaction product that includes an organosilicon compound. In particular, during the course of the reaction, the reaction mixture that includes components (A) and (B) includes increasing amounts of the organosilicon compound and decreasing amounts of components (A) and (B). Once the reaction is complete (e.g., one of components (A) and (B) is consumed, no additional organosilicon compound is prepared, etc.), the reaction mixture can be referred to as a reaction product that includes an organosilicon compound. Thus, the reaction product typically includes any remaining amounts of components (A), (B), (C), and optionally (D), as well as their decomposition and / or other reaction products (e.g., by-products and / or other materials), any carrier vehicle or solvent used, etc.

[0072] In certain embodiments, the method further comprises isolating and / or purifying the organosilicon compound from the reaction product. As used herein, isolating an organosilicon compound is typically defined as increasing the relative concentration of the organosilicon compound compared to other compounds combined with it (e.g., in the reaction product or a purified version thereof). Thus, as understood in the art, isolating / purifying may include removing other compounds from such combinations (i.e., reducing the amount of impurities / other components combined with the organosilicon compound in the reaction product, for example), and / or removing the organosilicon compound itself from the combination. Any suitable technique and / or protocol for isolation may be utilized. Examples of suitable isolation techniques include distillation, stripping / evaporation, extraction, filtration, washing, partitioning, phase separation, chromatography, and the like. As will be understood by those skilled in the art, any of these techniques may be used in combination (i.e., sequentially) with any other technique to isolate the organosilicon compound. It is understood that isolating may include purifying the organosilicon compound, and thus may be referred to as purifying the organosilicon compound. However, purifying the organosilicon compound may involve alternative and / or additional techniques compared to those utilized to isolate the organosilicon compound. Regardless of the particular technique selected, the isolation and / or purification of the organosilicon compound may be performed in line with the reaction itself (i.e., in-line) and therefore may be automated. In other cases, purification may be an independent procedure to which the reaction product, including the organosilicon compound, is subjected. In certain embodiments, the organosilicon compound is purified by venting and / or purging the reaction vessel and reaction product, for example, to remove any residual ethylene (B), hydrogen (H2), etc., prepared during the reaction. In some such embodiments, the reaction product is cooled during venting and / or purging.

[0073] In certain embodiments, the preparation method includes isolating the organosilicon compound from the reaction product via distillation, where the organosilicon compound is removed as a distillate from one or more components of the reaction product (e.g., catalyst (C)). The distillation is typically carried out at sub-atmospheric pressure and temperature (i.e., low temperature and reduced pressure). The reduced pressure and low temperature are selected by the skilled artisan in consideration of the selected reaction conditions and parameters, the components utilized, the organosilicon compound prepared, and the like. The reduced pressure is typically operated as a vacuum, but reduced pressures between vacuum and atmospheric pressure (i.e., 101.325 kPa) can be utilized. For example, the reduced pressure can be greater than 0 to 50 kPa, alternatively greater than 0 to 40 kPa, alternatively greater than 0 to 30 kPa, alternatively greater than 0 to 20 kPa, alternatively greater than 0 to 10 kPa, alternatively greater than 0 to 5 kPa, alternatively greater than 0 to 4 kPa, alternatively greater than 0 to 3 kPa, alternatively greater than 0 to 2 kPa (e.g., measured by mmHg).

[0074] Typically, the reaction product prepared by the reaction of components (A) and (B) includes a catalyst residue comprising a ruthenium complex. The ruthenium complex of the catalyst residue can be the same as, or substantially the same as, the Ru(0) complex utilized in the reaction or in component (C). Alternatively, the ruthenium complex of the catalyst residue can be a derivative of the Ru(0) complex utilized in or as component (C) of the reaction, for example, formed from the Ru(0) complex during the reaction.

[0075] In certain embodiments, the preparation method includes isolating the catalyst residue from the reaction mixture, for example using one or more of the above techniques. In some embodiments, isolating the organosilicon compound from the reaction product via distillation separates the catalyst residue by removing other components of the reaction product therefrom as a distillate.

[0076] The isolated catalyst residue can be utilized to catalyze another silylation reaction of components (A) and (B), for example, as described above, optionally in the presence of component (D). Thus, in certain embodiments, the preparation method includes using the catalyst residue (i.e., reusing catalyst (C)) to catalyze a further silylation reaction, which may be the same or different from the first reaction used to prepare the catalyst residue. For example, in some embodiments, the method includes two successive dehydrogenative coupling reactions using catalyst (C) and catalyst residue, respectively. In other embodiments, the method includes two successive hydrosilylation reactions using catalyst (C) and catalyst residue, respectively. However, the preparation method provides increased process utility by allowing rapid change in reaction selectivity (e.g., via changing the ethylene partial pressure in the reaction vessel) and by allowing change in process output (e.g., with respect to the organosilicon compound prepared). Thus, in certain embodiments, the method includes carrying out the silylation reaction described above, isolating catalyst (C) (or a derivative thereof, e.g., via collecting catalyst residue), and then using the isolated catalyst (C) or a derivative thereof to catalyze a further silylation reaction different from the first. For example, in some such embodiments, the silylation reaction is further defined as a dehydrogenative coupling and the further silylation reaction is further defined as a hydrosilylation. In other such embodiments, the silylation reaction is further defined as a hydrosilylation and the further silylation reaction is further defined as a dehydrogenative coupling.

[0077] It will be understood that recycling of catalyst (C) in this manner can be performed any number of times for any number of consecutive, independently selected silylation reactions, each of which may be the same or different from any other silylation reaction, In certain embodiments, catalyst (C) is recycled at least 1 time, alternatively at least 2 times, alternatively at least 3, 4, 5, 6, 7, 8, 9, or 10 times.

[0078] As introduced above, the preparation method prepares an organosilicon compound. As will be understood by those skilled in the art, the specific organosilicon compound prepared is a function of the specific hydridochlorosilane compound (A) utilized in the preparation method and the type of silylation reaction selected. More specifically, as will be understood in light of the above description of the structures of components (A) and (B) and the parameters of their reactions, the method prepares the organosilicon compound either as a dehydrogenative coupling product of the hydridochlorosilane compound (A) and ethylene (B) or as a hydrosilylation product. In either case, the hydridochlorosilane compound (A) forms the organosilicon compound's organochlorosilane backbone, and the ethylene (B) forms a vinyl or ethyl group bonded to the silicon atom of the organochlorosilane backbone.

[0079] Generally, organosilicon compounds are represented by the general formula Y-SiCl x R 3-x, where Y is a vinyl or 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 hydrocarbyl group having 1 to 18 carbon atoms (e.g., methyl, ethyl, etc.).

[0080] In some embodiments, Y is a vinyl group and x is 1 or 2, whereby the organosilicon compound can be further defined as an organovinylchlorosilane compound. For example, in some embodiments where the hydridochlorosilane compound (A) is further defined as a diorganohydridochlorosilane (e.g., when the subscript x is 1, the compound (A) has HSiClR2), the preparation method prepares the organosilicon compound as a diorganovinylchlorosilane compound having the formula (HCCH)SiClR2, where each R is as defined above. In other embodiments where the hydridochlorosilane compound (A) is further defined as an organohydridodichlorosilane (e.g., when the subscript x is 2, the compound (A) has the formula HSiClR), the preparation method prepares the organosilicon compound as an organovinyldichlorosilane compound having the formula (HCCH)SiClR2, where R is as defined above. In some embodiments, each R is an alkyl group, whereby the organosilicon compound is further defined as a dialkylvinylchlorosilane or an alkylvinyldichlorosilane. In one particular embodiment, each R is methyl (i.e., -CH), whereby the organosilicon compound is further defined as a dimethylvinylchlorosilane or a methylvinyldichlorosilane.

[0081] In certain embodiments, Y is an ethyl group and x is 1 or 2, whereby the organosilicon compound may be further defined as an organoethylchlorosilane compound. For example, in some embodiments where the hydridochlorosilane compound (A) is further defined as a diorganohydridochlorosilane (e.g., when the subscript x is 1, whereby compound (A) has the formula HSiClR2), the preparation method prepares the organosilicon compound as a diorganoethylchlorosilane compound having the formula (HCCH2)SiClR2, where each R is as defined above. In other embodiments where the hydridochlorosilane compound (A) is further defined as an organohydridodichlorosilane (e.g., when the subscript x is 2, compound (A) has the formula HSiClR), the preparation method prepares the organosilicon compound as an organoethyldichlorosilane compound having the formula (HCCH)SiClR, where R is as defined above. In some embodiments, each R is an alkyl group, whereby the organosilicon compound is further defined as a dialkylethylchlorosilane or an alkylethyldichlorosilane. In certain embodiments, each R is methyl (i.e., -CH), whereby the organosilicon compound is further defined as a dimethylethylchlorosilane or a methylethyldichlorosilane. It will be appreciated that the organosilicon compound may include a combination of such compounds, i.e., when two or more of the hydridochlorosilane compounds (A) are utilized in the preparation method.

[0082] The organosilicon compound prepared according to the preparation method can be utilized in various end-use applications, for example, as a separate component in compositions, including curable compositions, personal care or cosmetic compositions, etc. For example, when the prepared organosilicon compound contains at least one aliphatically unsaturated group per molecule (e.g., silicon-bonded vinyl group prepared from ethylene (B)), the organosilicon compound can be utilized in further alkene-based reactions, such as hydrosilylation reactions. For example, the organosilicon compound can be a component of a hydrosilylation curable composition. When the prepared organosilicon compound contains at least one ethyl group per molecule (e.g., silicon-bonded ethyl group prepared from ethylene (B)), the organosilicon compound can be utilized as an end-capping agent or building block to reduce the terminal methyl content of silicone compositions.

[0083] The following examples are intended to illustrate the embodiments described herein and should not be construed as limiting the scope of the invention in any way. Characterization Procedure

[0084] Gas Chromatography (GC)

[0085] Gas chromatography (GC) data is obtained using an Agilent 7890A gas chromatograph equipped with a Thermo Scientific TG-5HT column. Detection of eluting species is performed using a flame ionization detector (FID). Samples (1 μL) are injected onto the column, which is held at 40° C. for 8 minutes from the time of injection, after which the temperature is increased to 300° C. at a rate of 15° C. / min. Elution times are determined by injection of standards, and quantification of products is determined by integration of the eluted signal area. Exemplary standards (their elution times) include dimethylchlorosilane (1.90 min), methyldichlorosilane (1.93 min), vinyldimethylchlorosilane (2.44 min), vinylmethyldichlorosilane (2.79 min), ethyldimethylchlorosilane (2.62 min), and ethylmethyldichlorosilane (3.05 min). Ingredients and Materials

[0086] The specific ingredients utilized in the examples are set forth in Table 1 below. [Table 1] Examples 1-2: Preparation of vinyldimethylchlorosilane (ClSi(CH3)2(CHCH2))

[0087] Catalyst (C) (1.9 mg, 9.0 μmol Ru) is added to a Schlenk tube under ambient conditions. The tube is then evacuated and backfilled with nitrogen several times. Solvent (S-1) (12 mL) is then transferred to the tube via cannula, and the resulting mixture is stirred for 20 minutes with gentle heating to form a solution. The solution is then cooled to room temperature, hydridosilane (A) (100 μL, 900 μmol) is charged, and the resulting solution is transferred via cannula to a Fischer-Porter tube equipped with a stir bar and a manifold for introducing ethylene. The tube is then pressurized to 5 bar with ethylene and then vented. After pressurizing the tube with ethylene, it is vented four more times to substantially remove the nitrogen from the tube. The tube is then pressurized to 5 bar with ethylene and the solution is warmed to 100° C. and held with stirring for 2 hours. The solution is then cooled to −78° C. and the tube is vented. The solution is then transferred via cannula to a Schlenk tube and then to a distillation apparatus equipped with a collection vessel cooled to -78°C. The solution is then distilled at subatmospheric pressure and at a temperature of less than 25°C to remove a volatile product mixture containing the organosilicon compound as a distillate from the catalyst residue. The distillate is then warmed to room temperature and analyzed by gas chromatography to assess the conversion of hydridosilane (A) and the yield of organosilicon compound, the results of which are shown in Table 2 below. Comparative Example 1

[0088] The procedures described in Examples 1-2 above were repeated without the addition of catalyst (C) and the results are shown in Table 2 below. [Table 2]

[0089] In Examples 1-2, the organosilicon compound prepared is vinyldimethylchlorosilane. As shown in Table 2, the exemplary method provides nearly complete conversion of the hydridosilane starting material with good yields of dehydrocoupling products. In each of Examples 1-2, ethyldimethylchlorosilane is identified as the major by-product, proving hydrosilylation as a competing reaction under the conditions utilized. As also shown in Table 2 above, in the absence of catalyst (C), no significant conversion of hydridosilane (A-1) is observed (see Comparative Example 1). Examples 3-11: Preparation of vinyldimethylchlorosilane (ClSi(CH3)2(CHCH2))

[0090] Catalyst (C-1) (1.9 mg, 9.0 μmol Ru) and ligand (L) are added to a Schlenk tube under ambient conditions. The tube is then evacuated and backfilled with nitrogen several times. Solvent (S) (12 mL) is then transferred to the tube via cannula and the resulting mixture is stirred for 20 minutes with gentle heating to form a solution. The solution is then cooled to room temperature and charged with hydridosilane (A-1) (100 μL, 900 μmol) and the resulting mixture is transferred via cannula to a Fischer-Porter tube equipped with a stir bar and a manifold for introducing ethylene. The tube is then pressurized to 5 bar with ethylene and then vented. After pressurizing the tube with ethylene, it is vented four more times to substantially remove the nitrogen from the tube. The tube is then pressurized to 5 bar with ethylene and the solution is warmed to 100° C. and held with stirring for 2 hours. The solution is then cooled to −78° C. and the tube is vented. The solution is then transferred via cannula to a Schlenk tube and then to a distillation apparatus equipped with a collection vessel cooled to -78°C. The solution is then distilled at subatmospheric pressure and below 25°C to remove a volatile product mixture containing the organosilicon compound as a distillate from the catalyst residue. The distillate is then warmed to room temperature and analyzed by gas chromatography to evaluate the conversion of hydridosilane (A-1) and the yield of organosilicon compound. The specific parameters and evaluation results of Examples 3-11 are shown in Table 3 below. [Table 3]

[0091] In Examples 3-11, the organosilicon compound prepared is vinyldimethylchlorosilane. As shown in Table 3 above, the exemplary process provides nearly complete conversion of the hydridosilane starting material with good yields of the dehydrocoupling product. In each of Examples 3-11, ethyldimethylchlorosilane is identified as the major by-product, demonstrating hydrosilylation as a competing reaction under the conditions utilized. Examples 12-14: Preparation of vinyldimethylchlorosilane (ClSi(CH3)2(CHCH2))

[0092] Catalyst (C-1) (1.9 mg, 9.0 μmol) and ligand (L) are added to a Schlenk tube under ambient conditions. The tube is then evacuated and backfilled with nitrogen several times. Solvent (S-1) (12 mL) is then transferred to the tube via cannula and the resulting mixture is stirred for 20 minutes with gentle heating to form a solution. The solution is then cooled to room temperature and charged with hydridosilane (A-1) (100 μL, 900 μmol) and sacrificial olefin (D-1) and the resulting mixture is transferred via cannula to a Fischer-Porter tube equipped with a stir bar and a manifold for introducing ethylene. The tube is then pressurized to 5 bar with ethylene and then vented. After pressurizing the tube with ethylene, it is vented four more times to substantially remove the nitrogen from the tube. The tube is then pressurized to 5 bar with ethylene and the solution is warmed to 100° C. and held with stirring for 2 hours. The solution is then cooled to −78° C. and the tube is vented. The solution is then transferred via cannula to a Schlenk tube and then to a distillation apparatus equipped with a collection vessel cooled to -78°C. The solution is then distilled at subatmospheric pressure and below 25°C to remove a volatile product mixture containing organosilicon compounds as a distillate from the catalyst residue. The distillate is then warmed to room temperature and analyzed by gas chromatography to evaluate the conversion of hydridosilane (A-1) and the yield of organosilicon compounds. The parameters and evaluation results of Examples 12-14 are shown in Table 4 below. [Table 4]

[0093] In Examples 12-14, the organosilicon compound prepared is vinyldimethylchlorosilane. As shown in Table 4 above, the exemplary process provides nearly complete conversion of the hydridosilane starting material with good yields of the dehydrocoupling product. In each of Examples 12-14, ethyldimethylchlorosilane is identified as the major by-product, demonstrating hydrosilylation as a competing reaction under the conditions utilized. Examples 15-20: Preparation of vinylmethyldichlorosilane (Cl2MeSiCHCH2)

[0094] Catalyst (C-1) (2.1 mg, 9.6 μmol) and ligand (L) are added to a Schlenk tube under ambient conditions. The tube is then evacuated and backfilled with nitrogen several times. Solvent (S) (12 mL) is then transferred to the tube via cannula and the resulting mixture is stirred for 20 minutes with gentle heating to form a solution. The solution is then cooled to room temperature and charged with hydridosilane (A-2) (100 μL, 900 μmol) and the resulting mixture is transferred via cannula to a Fischer-Porter tube equipped with a stir bar and a manifold for introducing ethylene. The tube is then pressurized to 5 bar with ethylene and then vented. After pressurizing the tube with ethylene, it is vented four more times to substantially remove the nitrogen from the tube. The tube is then pressurized to 5 bar with ethylene and the solution is warmed to 100° C. and held with stirring for a time (T). The solution is then cooled to −78° C. and the tube is vented. The solution is then transferred via cannula to a Schlenk tube and then to a distillation apparatus equipped with a collection vessel cooled to -78°C. The solution is then distilled at subatmospheric pressure and below 25°C to remove a volatile product mixture containing the organosilicon compound as a distillate from the catalyst residue. The distillate is then warmed to room temperature and analyzed by gas chromatography to evaluate the conversion of hydridosilane (A-2) and the yield of organosilicon compound. The specific parameters and evaluation results of Examples 15-20 are shown in Table 5 below. Comparative Example 2

[0095] The procedures described above in Examples 15-20 were repeated without the addition of catalyst (C) and the results are shown in Table 5 below. [Table 5]

[0096] In Examples 15-20, the organosilicon compound prepared is dichloromethylvinylsilane. As shown in Table 5 above, the exemplary process provides for the conversion of the hydridosilane starting material to the dehydrocoupling product in reasonable yield. In the absence of catalyst (C), no significant conversion of hydridosilane (A-2) is observed (see Comparative Example 2). In each of Examples 15-20, ethylmethyldichlorosilane is identified as the major by-product, demonstrating hydrosilylation as a competing reaction under the conditions utilized. Examples 21-22: Continuous preparation of vinyldimethylchlorosilane (ClSi(CH3)2(CHCH2))

[0097] Example 21: First preparation

[0098] In the first preparation, hydridosilane is dehydrogenatively bonded to ethylene using a catalyst to obtain an organosilicon compound (Example 21). Specifically, catalyst (C-1) (1.9 mg, 9.0 μmol) is added to a Schlenk tube under ambient conditions. The tube is then evacuated and backfilled with nitrogen several times. Solvent (S-1) (12 mL) is then transferred to the tube via a cannula, and the resulting mixture is stirred for 20 minutes with gentle heating to form a solution. The solution is then cooled to room temperature, hydridosilane (A-1) (100 μL, 900 μmol) is charged, and the resulting solution is transferred via a cannula to a Fischer-Porter tube equipped with a stir bar and a manifold for introducing ethylene. The tube is then pressurized to 5 bar with ethylene and then vented. After pressurizing the tube with ethylene, it is vented four more times to substantially remove the nitrogen from the tube. The tube is then pressurized to 5 bar with ethylene and the solution is warmed to 100° C. and held with stirring for 2 hours. The solution is then cooled to −78° C. and the tube is vented. The solution is then transferred via cannula to a Schlenk tube and then to a distillation apparatus equipped with a collection vessel cooled to −78° C. The solution is then distilled to a volume of about 2 mL at subatmospheric pressure and a temperature of less than 25° C. to remove a first product mixture containing organosilicon compounds as a distillate, leaving behind a concentrated catalyst residue, which is set aside. The distillate is then warmed to room temperature and analyzed by gas chromatography, giving the following results: >99% conversion of dimethylchlorosilane, yield of vinyldimethylchlorosilane=75%, and ethyldimethylchlorosilane as the major by-product.

[0099] Example 22: Second preparation

[0100] In a second preparation, the hydridosilane is dehydrogenatively coupled to ethylene using the recycled catalyst to obtain an organosilicon compound (Example 22). Specifically, the concentrated catalyst residue set aside in Example 21 above is transferred to a Schlenk tube and diluted to 12 mL with solvent (S-1). The resulting mixture is then utilized in the procedure of Example 21 above to obtain a second product mixture containing an organosilicon compound, which is analyzed by gas chromatography to evaluate the conversion of the hydridosilane (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%, and ethyldimethylchlorosilane as the main by-product. Examples 23-32: Continuous preparation of vinyldimethylchlorosilane (ClSi(CH3)2(CHCH2))

[0101] Example 23: First preparation

[0102] In the first preparation, hydridosilane is dehydrogenatively bonded to ethylene using a catalyst to obtain an organosilicon compound (Example 23). Specifically, catalyst (C-1) (1.9 mg, 9.0 μmol) and ligand (L-2) (6.3 mg, 18 μmol) are added to a Schlenk tube under ambient conditions. The tube is then evacuated and refilled with nitrogen several times. Solvent (S-1) (12 mL) is then transferred to the tube via a cannula, and the resulting mixture is stirred for 20 minutes with gentle heating to form a solution. The solution is then cooled to room temperature, hydridosilane (A-1) (100 μL, 900 μmol) is charged, and the resulting solution is transferred via a cannula to a Fischer-Porter tube equipped with a stir bar and a manifold for introducing ethylene. The tube is then pressurized to 5 bar with ethylene and then vented. After pressurizing the tube with ethylene, it is vented four more times to substantially remove the nitrogen from the tube. The tube is then pressurized to 5 bar with ethylene and the solution is warmed to 100° C. and held with stirring for 2 hours. The solution is then cooled to −78° C. and the tube is vented. The solution is then transferred via cannula to a Schlenk tube and then to a distillation apparatus equipped with a collection vessel cooled to −78° C. The solution is then distilled to a volume of about 2 mL at subatmospheric pressure and a temperature of less than 25° C. to remove a first product mixture containing organosilicon compounds as a distillate, leaving behind a concentrated catalyst residue, which is set aside. The distillate is then warmed to room temperature and analyzed by gas chromatography, the results of which are shown below in Table 6.

[0103] Example 24: Second preparation

[0104] The concentrated catalyst residue set aside in Example 23 above is transferred to a Schlenk tube and diluted to 12 mL with solvent (S-1). The resulting mixture is then used in a second preparation according to the procedure of Example 23 to obtain a second product mixture comprising an organosilicon compound and a second concentrated catalyst residue (Example 24). The second product mixture is then warmed to room temperature and analyzed by gas chromatography, the results of which are shown in Table 6 below.

[0105] Examples 25 to 32: Preparation of Nos. 3 to 10

[0106] The procedure of Example 25 above is repeated successively over a series of eight preparations using the concentrated catalyst residue prepared in the previous preparation (i.e., starting from the second concentrated catalyst residue prepared in Example 24), to obtain eight product mixtures containing organosilicon compounds (Examples 25-32).The product mixtures of Examples 25-32 are each analyzed by gas chromatography, and the results are shown in Table 6 below. [Table 6]

[0107] In Examples 23-32, the organosilicon compound prepared is vinyldimethylchlorosilane, with ethyldimethylchlorosilane identified as the major by-product in each preparation. As shown in Table 6 above, the exemplary methods and materials provide nearly complete conversion of the hydridosilane starting material with good yields of the dehydrocoupling product. Furthermore, the reaction products are easily removed from the catalyst residue, which can be conveniently recycled in successive preparations without additional processing steps or loss of conversion or yield. Examples 33-34: Selective preparation of vinyl and ethyl functionalized silanes

[0108] Example 33: Selective Preparation of Vinyldimethylchlorosilane (ClSi(CH3)2(CHCH2))

[0109] In an inerted glove box, solvent (S-1) (30.15 g) is weighed into a glass screw-top vessel. The vessel is then loaded with catalyst (C-1) (26 mg) and a magnetic stir bar, sealed, and placed on a magnetic stir plate from the glove box. The mixture is stirred and heated to 50° C. to dissolve the catalytic metal complex, then returned to the glove box and allowed to cool to ambient temperature. Hydridosilane (A-1) (13.54 g) is then added to the solution to obtain a reaction mixture, which is then loaded with nonane (1.13 g) as an internal reference standard for gas chromatographic analysis. A reference sample (1 g aliquot) of the reaction mixture is placed in a glass vial, diluted with solvent (S-1) (4 g), and analyzed to determine the starting concentration of hydridosilane (A-1) in the reaction mixture.

[0110] The reaction mixture is transferred to a stainless steel sample cylinder, which is 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, then purged with nitrogen for 10 minutes. The reaction mixture is transferred to the reactor via nitrogen pressure (10 psig, approximately 68.9 kPa), and the reactor is purged with ethylene (3×100 psig, approximately 689 kPa; stirred for 1 minute). The reactor is then pressurized with ethylene (610 psig, approximately 4,206 kPa), stirred (350 rpm) until saturated (stable pressure), sealed, heated to 40° C. with stirring, and held. After a 10-minute stabilization period, the reactor is then heated to 100° C. (2° C. / min ramp to prevent temperature overshoot) and held at that temperature for 90 minutes. The reactor is then cooled to room temperature (external fan), depressurized, and then purged three times with nitrogen (100 psig, approx. 689 kPa). The reactor is then connected to a nitrogen flow (10 psig, approx. 68.9 kPa) which is used to transfer the reaction mixture into a stainless steel sample cylinder. The cylinder is sealed and transported to an inerted glove box and the contents are transferred into a glass vial. A reference sample (1 g aliquot) of the reaction mixture is placed in a glass vial, diluted with solvent (S-1) (4 g) and analyzed by gas chromatography to evaluate the conversion of hydridosilane (A-1) and the yield of organosilicon compounds, with the following results: yield of vinyldimethylchlorosilane = 84%, with ethyldimethylchlorosilane (13.5%) as the main by-product.

[0111] Example 33: Selective Preparation of Ethyldimethylchlorosilane (ClSi(CH3)2(CH2CH3))

[0112] In an inerted glove box, solvent (S-1) (30.15 g) is weighed into a glass screw-top vessel. The vessel is then charged with catalyst (C-1) (25 mg) and a magnetic stir bar, sealed, and placed on a magnetic stir plate from the glove box. The mixture is stirred and heated to 50° C. to dissolve the catalytic metal complex, then returned to the glove box and allowed to cool to ambient temperature. Hydridosilane (A-1) (13.50 g) is then added to the solution to obtain a reaction mixture, which is then charged with nonane (1.18 g) as an internal reference standard for gas chromatographic analysis.

[0113] A reference sample (1 g aliquot) of the reaction mixture is placed in a glass vial, diluted with solvent (S-1) (4 g), and analyzed to determine the starting concentration of hydridosilane (A-1). The reaction mixture is transferred to a stainless steel sample cylinder, which is 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 is transferred to the reactor via nitrogen pressure (10 psig, approximately 68.9 kPa), and the reactor is purged with ethylene (3 x 100 psig, approximately 689 kPa; stirred for 1 minute). The reactor is then pressurized with ethylene (200 psig, approximately 1,379 kPa), stirred (450 rpm) until saturated (stable pressure), sealed, heated to 40°C with stirring (350 rpm), and held. After a 10 min stabilization period, the reactor is heated to 100°C (2°C / min ramp to prevent temperature overshoot) and held at that temperature for 140 min. The reactor is then cooled to room temperature (external fan), depressurized, and then purged three times with nitrogen (100 psig, approx. 689 kPa). The reactor is then connected to a nitrogen flow (10 psig, approx. 68.9 kPa), which is used to transfer the reaction mixture into a stainless steel sample cylinder. The cylinder is sealed and transported to an inerted glove box, and the contents are transferred into a glass vial. A reference sample (1 g aliquot) of the reaction mixture is placed in a glass vial, diluted with solvent (S-1) (4 g) and analyzed by gas chromatography to evaluate the conversion of hydridosilane (A-1) and the yield of organosilicon compounds, giving the following results: dimethylchlorosilane = 73% (23% of the starting dimethylchlorosilane remains unreacted), yield of ethyldimethylchlorosilane = 64%, with vinyldimethylchlorosilane (13%) as the main by-product.

[0114] The above description relates to the 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. Thus, the present disclosure is presented for illustrative purposes and should not be construed as an exhaustive description of all embodiments of the disclosure or to limit 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 form using the articles "a," "an," "the," or "the" should not be construed as limiting the element to the singular form. Furthermore, it should be understood that the terms "right angle," "orthogonal," "vertical," and "parallel" are generally used herein in a relative, rather than absolute, sense. Furthermore, it should be understood that terms such as "substantially," "about," and "essentially" indicate slight deviations in the property being modified. Such deviations may be 0-10%, alternatively 0-5%, or alternatively 0-3% of a particular property.

Claims

1. 1. A method for preparing an organosilicon compound comprising the steps of:

1. A method comprising: reacting (A) a hydridochlorosilane compound and (B) ethylene via silylation in the presence of (C) a catalyst comprising a Ru(0) complex, the Ru(0) complex comprising a triruthenium complex and a phosphorus ligand, thereby preparing the organosilicon compound.

2. The method of claim 1, further comprising preparing the catalyst (C). (i) The phosphorus ligand is represented by the general formula R １ ２ PR ２ wherein each R １ is an independently selected substituted or unsubstituted aryl, aralkyl, or cycloalkyl group; R ２ But, R １ or an alkaryl group, or (ii) the phosphorus ligand has a molecular weight of 2,060 to 2,090 cm －１ or (iii) the phosphorus ligand comprises a Tolman cone angle of 115 to 185°; or (iv) any combination of (i) to (iii).

4. 4. The method of any one of claims 1 to 3, wherein the silylation is further defined as a dehydrogenative coupling of the hydridochlorosilane compound (A) with the ethylene (B) such that the organosilicon compound is prepared as a vinylchlorosilane compound, and the dehydrogenative coupling is carried out at a stoichiometric ratio of hydridochlorosilane compound (A) to ethylene (B) of at least 1:2 (A):(B).

5. 5. The method of claim 4, wherein the Ru(0) complex of the catalyst (C) comprises an organophosphite ligand, the organophosphite ligand comprising a substituted or unsubstituted triarylphosphite.

6. 5. The process of claim 4, wherein the dehydrocoupling of components (A) and (B) is carried out in the presence of (D) an olefinic compound having an unsaturated aliphatic group.

7. 4. The method of any one of claims 1 to 3, wherein the silylation is further defined as the hydrosilylation of the hydridochlorosilane compound (A) with the ethylene (B) such that the organosilicon compound is prepared as an ethylchlorosilane compound, and the hydrosilylation is carried out at a stoichiometric ratio of hydridochlorosilane compound (A) to ethylene (B) (A):(B) of less than 1:

2.

8. The organosilicon compound is prepared in a reaction product, the process comprising: (I) isolating the catalyst (C) from the reaction product; and 8. The method of any one of claims 1 to 7, further comprising: (II) using the isolated catalyst (C) to catalyze further silylation reactions.

9. 9. The process according to any one of claims 1 to 8, wherein the silylation is carried out (i) at an elevated temperature of 60 to 200°C, (ii) at a pressure of from atmospheric pressure to 110 bar, (iii) in the presence of a solvent, (iv) with a concentration of said catalyst (C) in an amount of 0.0001 to 5 wt.%, based on the total amount of component (A) employed, or (v) any combination of (i) to (iv).

10. 10. The method of any one of claims 1 to 9, having (i) a conversion of hydridochlorosilane compound (A) of at least 85%, (ii) a yield of said organosilicon compound of at least 75%, or (iii) both (i) and (ii).

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