Method for the redistribution of silicon-bonded groups

Abstract

The present disclosure provides a method of preparing a target compound. The method includes the step of combining (A) an organosilicon component and (B) a catalyst including a boron cluster to give a mixture. The method further includes preparing a reaction mixture including the target compound from the mixture. The organosilicon component (A) includes (A1) a first organosilicon compound having a silicon-bonded C1-C4 alkyl group. When the first organosilicon compound (A1) does not include a silicon-bonded halogen atom, the organosilicon component (A) includes a second organosilicon compound (A2) including at least one silicon-bonded halogen atom. The disclosure further provides a reaction product prepared according to the method.

Description

METHOD FOR THE REDISTRIBUTION OF SILICON-BONDED GROUPS CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and all advantages of U. S. Provisional Patent Application No. 63 / 716,231 filed on 04 November 2024, and U. S. Provisional Patent Application No. 63 / 784,573 filed on 07 April 2025, the content of which is incorporated herein by reference.FIELD OF THE INVENTION

[0002] The present disclosure relates generally to a method of facilitating an exchange of one silicon-bonded alkyl group of a first silane molecule with a silicon-bonded halogen atom of a second silane molecule, and more specifically, to a method of exchanging the silicon-bonded alkyl group with a silicon-bonded halogen atom by combining an organosilicon component and a catalyst comprising a boron cluster, and a reaction product comprising a target compound prepared in accordance with the same.DESCRIPTION OF THE RELATED ART

[0003] Catalysts are known in the art and are utilized in myriad industrial and commercial processes. Although most industrial and commercial catalysts have been identified and optimized over time, energy requirements and desire for efficiency remain significant.

[0004] For example, catalysts are utilized in making and ultimately using various silanes and organosilicon compounds. However, the creation of a silicon-carbon bond requires significant energy. To form silicon-methyl bonds, SiO2 is first carbothermally reduced to Si, which is thermodynamically inefficient due to energy losses and incomplete conversion of raw materials. Si is then reacted with MeCI in the presence of a copper catalyst package in the Mueller-Rochow direct process.

[0005] Not only is the direct process energy intensive, but there’s little control of yield of byproducts. The main product of the direct process is dimethylchlorosilane (-85%), with the next highest components being MeSiCl3 and MesSiCL Industry often desires more MesSiCI as an end-blocker for organopolysiloxane polymerization. MeSiCl3 is typically produced in excess. Increasing production of MesSiCI via the direct process also results in greater production of MeSiCIs.BRIEF SUMMARY

[0006] The present disclosure provides a method of preparing a target compound. The method comprises the step of combining (A) an organosilicon component and (B) a catalyst comprising a boron cluster to give a mixture. The method further comprises preparing a reaction mixture comprising the target compound from the mixture. The organosilicon component (A) comprises (A1) a first organosilicon compound having at least one silicon-bonded C1-C4 alkyl group and optionally at least one silicon-bonded halogen atom. When the first organosiliconcompound (A1) does not include a silicon-bonded halogen atom, the organosilicon component (A) further comprises a second organosilicon compound (A2) including at least one silicon-bonded halogen atom.

[0007] The target compound is different from the first organosilicon compound (A1 ) and, if utilized, the second organosilicon compound (A2). The catalyst (B) is capable of facilitating the exchange of one silicon-bonded alkyl group of a first silane molecule with a silicon-bonded halogen atom of a second silane molecule.

[0008] The present disclosure further provides a reaction product prepared according to the method.DETAILED DESCRIPTION

[0009] A method of preparing a target compound is disclosed. The target compound is generally an organosilicon compound, and can be referred to as the target organosilicon compound. The target organosilicon compound can be utilized in myriad end use applications and can be selectively prepared via the inventive method in desirable yields.

[0010] The method comprises combining (A) an organosilicon component and (B) a catalyst comprising a boron cluster to give a mixture. The organosilicon component (A) and the catalyst (B) can be combined in any order of addition, optionally via masterbatches, and optionally under shear or mixing.

[0011] The organosilicon component (A) comprises (A1) a first organosilicon compound having at least one silicon-bonded C1-C4 alkyl group and optionally at least one silicon-bonded halogen atom. When the first organosilicon compound (A1) does not include a silicon-bonded halogen atom, the organosilicon component (A) further comprises a second organosilicon compound (A2) including at least one silicon-bonded halogen atom. The halogen atom is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I). In certain embodiments, the halogen atom is fluorine (F), chlorine (Cl), or bromine (Br). In specific embodiments, the halogen atom is Cl. Examples of suitable C1-C4 alkyl groups include methyl, ethyl, propyl (e.g. iso-propyl and / or n-propyl), and butyl (e.g. isobutyl, n-butyl, tert-butyl, and / or sec-butyl). In certain embodiments, the C1-C4 alkyl groups are not branched. In specific embodiments, the C1-C4 alkyl groups are independently methyl, ethyl, or propyl, alternatively methyl or ethyl, alternatively methyl.

[0012] Thus, in the organosilicon component (A), there is at least one silicon-bonded C1-C4 alkyl group and at least one silicon-bonded halogen atom, which may be present in the same or different molecules, as described below. For example, the organosilicon component (A) generally includes a plurality of molecules. The first organosilicon compound (A1) of the organosilicon component (A) may include different species of organosilicon compounds having at least one silicon-bonded C1-C4 alkyl group and optionally at least one silicon-bonded halogen atom. When the molecules of the first organosilicon compound (A1) do not include any silicon-bonded halogen atoms, then the organosilicon component (A) further comprises the secondorganosilicon compound (A2) which includes at least one silicon-bonded halogen atom. Like the first organosilicon compound (A1), the second organosilicon compound (A2) of the organosilicon component (A) may include different species of organosilicon compounds having at least one silicon-bonded halogen atom.

[0013] Typically, the first organosilicon compound (A1) and the second organosilicon compound (A2), if utilized, are monosilanes, i.e., include one silicon atom. More specifically, the first organosilicon compound (A1) and the second organosilicon compound (A2), if utilized, are typically free from siloxane bonds (-Si-O-Si-) or silicon-silicon bonds (-Si-Si-).

[0014] In certain embodiments, the first organosilicon compound (A1) is free from any silicon-bonded groups or atoms other than C1-C4 alkyl groups and halogen atoms. In such embodiments, the first organosilicon compound (A1) is free from, for example, silicon-bonded hydrogen atoms. In further embodiments, the organosilicon component (A) is free from organosilicon compounds having any silicon-bonded groups or atoms other than C1-C4 alkyl groups and halogen atoms, i.e., in such embodiments, if the organosilicon component (A) further comprises the second organosilicon compound (A2), the second organosilicon compound (A2) is also free from, for example, silicon-bonded hydrogen atoms.

[0015] In one embodiment, the first organosilicon compound (A1) includes both a silicon-bonded C1-C4 alkyl group and at least one silicon-bonded halogen atom. In some such embodiments, the first organosilicon compound (A1) has the general formula RxHyQzSi, where each R is an independently selected alkyl group having from 1 to 4 carbon atoms, each Q is an independently selected halogen atom, 1<x<3, 0<y<2, 1<z<3 and x+y+z=4. Examples of halogen atoms and C1-C4 alkyl groups are described above.

[0016] In specific embodiments, subscript y is 0 such that the first organosilicon compound (A1) has the general formula RxQzSi, where1≤x≤3, 1≤z≤3 and x+z=4. For example, when x is 1, z is 3, R is Me, and Q is Cl, the first organosilicon compound has formula MeSiCl3. When x is 2, z is 2, R is Me, and Q is Cl, the first organosilicon compound has formula Me2SiCl2.

[0017] The first organosilicon compound (A1) can include two or more different organosilicon compounds that differ in structure. By way of example, the first organosilicon compound (A1) can comprise a mixture of MeSiCl3and Me2SiCl2.

[0018] In other embodiments, as described above, the first organosilicon compound (A1) can be free of silicon-bonded halogen atoms. In such embodiments, the first organosilicon compound can have the formula R4Si, where each R is independently selected and defined above.

[0019] When the first organosilicon compound (A1) is free of silicon-bonded halogen atoms, the organosilicon component (A) further comprises the second organosilicon compound (A2). The second organosilicon compound (A2) includes at least one silicon-bonded halogenatom, but is not otherwise limited. Typically, any silicon-bonded groups or atoms in the second organosilicon compound (A2) that are not silicon-bonded halogen atoms are silicon-bonded C1-C4 alkyl groups, as described above for the first organosilicon compound (A1). For example, the second organosilicon compound (A2) can include one silicon-bonded halogen atom and three silicon-bonded C1-C4 alkyl groups, two silicon-bonded halogen atoms and two silicon-bonded C1-C4 alkyl groups, three silicon-bonded halogen atoms and one silicon-bonded C1-C4 alkyl group, or four silicon-bonded halogen atoms. The halogen atoms and C1-C4 alkyl groups are independently selected. The second organosilicon compound (A2) can include two or more different organosilicon compounds that differ in structure. By way of example, the second organosilicon compound (A2) can comprise a mixture of MeSiCl3 and Me2SiCl2.

[0020] Although both the first and second organosilicon compounds (A1), (A2), can each independently comprise blends of different organosilicon compounds that differ from one another in structure, the first organosilicon compound (A1) is different from and does not encompass the same species of molecules as the second organosilicon compound (A2). For example, although it is described above that either the first organosilicon compound (A1) or the second organosilicon compound (A2) can comprise a mixture of MeSiCl3 and Me2SiCl2, the first and second organosilicon compounds (A1), (A2) do not simultaneously comprise or include the same molecules or compounds. If the second organosilicon compound (A2) is a mixture of MeSiCIs and Me2SiCl2, it’s typically because the first organosilicon compound (A1) is free of silicon-bonded halogen atoms, e.g. is R4Si such that the first and second organosilicon compounds (A1), (A2) remain different from one another.

[0021] In certain embodiments, the first organosilicon compound (A1) comprises R4Si, RSiQ3 or R2SiQ2, where each R and each Q is independently selected and defined above. When the first organosilicon compound (A1) comprises R4Si, the organosilicon component further comprises the second organosilicon compound (A2). In such embodiment, the second organosilicon compound (A2) can be or comprises RSiQ3, R2SiQ2, or SiQ4, where each R and each Q is independently selected and defined above.

[0022] In one embodiment, the first organosilicon compound (A1) comprises, consists essentially of, or consists of RSiQ3, e.g. MeSiCIs, where Me indicates methyl.

[0023] In another embodiment, the first organosilicon compound (A1 ) comprises, consists essentially of, or consists of R2SiQ2, e.g. Me2SiCl2, where Me indicates methyl.

[0024] In yet another embodiment, the first organosilicon compound (A1) comprises RSiQ3, e.g. MeSiCl3, where Me indicates methyl, and wherein the organosilicon component (A) further comprises the second organosilicon compound (A2). The second organosilicon compound (A2) in such embodiments may be, for example, R2SiQ2, e.g. Me2SiCl2. Asunderstood in the art, in embodiments in which the organosilicon component comprises both RSiQ3 and R2SiQ2, it can be considered that the first organosilicon compound (A1) comprises a mixture of RSiQ3 and R2SiQ2, as each molecule includes a silicon-bonded C1-C4 alkyl group and a silicon-bonded halogen atom. Alternatively, in such embodiments, it can be considered that the first organosilicon compound (A1) comprises RSiQ3 and the second organosilicon compound (A2) comprises R2SiQ2.

[0025] In yet another embodiment, the first organosilicon compound (A1) comprises R4Si, e.g. Me4Si, where Me indicates methyl, and wherein the organosilicon component (A) further comprises the second organosilicon compound (A2). The second organosilicon compound (A2) in such embodiments may be, for example, RSiQ3, e.g. MeSiCl3.

[0026] In other embodiments, the first organosilicon compound (A1) comprises RSiQ3, e.g. MeSiCl3, where Me indicates methyl, and wherein the organosilicon component (A) further comprises the second organosilicon compound (A2). The second organosilicon compound (A2) in such embodiments may be, for example, R3SiQ, e.g. Me3SiCl. As understood in the art, in embodiments in which the organosilicon component comprises both RSiQ3and R3SiQ, it can be considered that the first organosilicon compound (A1) comprises a mixture of RSiQ3and R3SiQ, as each molecule includes a silicon-bonded C1-C4 alkyl group and a silicon-bonded halogen atom. Alternatively, in such embodiments, it can be considered that the first organosilicon compound (A1) comprises RSiQ3 and the second organosilicon compound (A2) comprises R3SiQ.

[0027] When the organosilicon component (A) includes both the first and second organosilicon compounds (A1), (A2), the first and second organosilicon compounds (A1), (A2) may be utilized in various amounts or ratios, which can be influenced by myriad factors, including the desired structure of the target organosilicon compound.

[0028] In certain embodiments, the second organosilicon compound (A2) is utilized in a molar excess relative to the first organosilicon compound (A1). For example, the second organosilicon compound (A2) can be used in a molar ratio of from greater than 1:1 to 100:1, alternatively from greater than 1: 1 to 80: 1, alternatively from greater than 1: 1 to 60: 1, alternatively from greater than 1: 1 to 40: 1, alternatively from greater than 1: 1 to 20: 1, alternatively from greater than 1:1 to 10:1, relative to the first organosilicon compound (A1). In other embodiments, however, the second organosilicon compound (A2) is utilized in a molar excess relative to the first organosilicon compound (A1). In such embodiments, the molar ratios above apply in inverted form, i.e., the ratios above apply as the ratio of the first organosilicon compounds (A1) to the second organosilicon compound (A2). Alternatively still, stoichiometric ratios can be utilized.

[0029] The catalyst (B) comprises a boron cluster and is capable of facilitating theexchange of one silicon-bonded alkyl group of a first silane molecule with a silicon-bonded halogen atom of a second silane molecule. The catalyst (B) is not limited so long as the catalyst comprises the boron cluster and is capable of facilitating the exchange of one silicon-bonded alkyl group of a first silane molecule with a silicon-bonded halogen atom of a second silane molecule. The catalyst (B) may be formed in situ in the presence of the organosilicon component (A). For example, the composition may utilize a pre-catalyst, which converts to a catalytically active form in situ to give the catalyst (B). In such embodiments, the pre-catalyst may be any suitable pre-catalyst that forms the catalytically active form of the catalyst (B) in situ.

[0030] In certain embodiments, the catalyst (B) comprises a salt comprising one dianion having a charge of -2 and two cations, wherein the one dianion comprises the boron cluster.

[0031] In specific embodiments, the one dianion has the formula (BaXbYc)2-, where subscript a is 10 or 12, subscripts b and c are each independently selected integers greater than zero and b+c=a, wherein X and Y may be the same or different, and each X and each Y is independently selected from halogen atoms; H; hydrocarbyl groups; -SiR^ groups, where each R1 is independently an alkyl group or a halogen atom; -OR2groups, where each R2is H or an independently selected alkyl group; methanesulfonyloxy (mesyloxy) groups, tosyloxy groups, triflyloxy groups, nitro-phenylsulfonyloxy (nosyloxy) groups, bromo-phenylsulfonyloxy (brosyloxy) groups, and OC(O)R3 groups, where R^ is an alkyl group.

[0032] The halogen atoms represented by X and Y (or R^ ) can be fluorine (F), chlorine (Cl), bromine (Br), iodine (I). In certain embodiments, when X and / or Y is a halogen atom, the halogen atom is Br, Cl, or F. In yet other embodiments, when X and / or Y is a halogen atom, the halogen atom is Cl or F. In specific embodiments, when X and / or Y is a halogen atom, the halogen atom is Cl.

[0033] In one embodiment, at least one X and / or Y is an -SiR^ groups, where each R^ is independently an alkyl group or a halogen atom. When each R^ is methyl, the -SiR^ group is a trimethylsilyl group. When two of R”* are methyl and the other is chlorine, the -SiR^ group is a dimethylchlorosilyl group. When all of R are chlorine, the -SiR^ group is a trichlorosilyl group.

[0034] In one embodiment, at least one X and / or Y is an -OR2group, where R2is H, i.e., at least one X and / or Y is an OH group. In other embodiments when at least one X and / or Y is an -OR2group, each R2is an independently selected alkyl group. In such embodiments, each R2may be linear, branched, cyclic (e.g. cycloalkyl), or combinations thereof. In certain embodiments, each R2is linear or branched. In specific embodiments, each R2is linear.

[0035] In one embodiment, at least one X and / or Y is a hydrocarbyl group, which are independently selected when more than one X and Y, individually or collectively, is a hydrocarbylgroup. Suitable hydrocarbyl groups may independently be linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups encompass aryl groups as well as saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may be monocyclic or polycyclic. Linear and branched hydrocarbyl groups may independently be saturated or unsaturated. One example of a combination of a linear and cyclic hydrocarbyl group is an alkyl substituted aryl group. By “substituted,” it is meant that one or more hydrogen atoms may be replaced with atoms other than hydrogen (e.g., a halogen atom, such as chlorine, fluorine, bromine, etc.) or groups other than hydrogen. Suitable alkyl groups are exemplified by, but not limited to, methyl, ethyl, propyl (e.g., iso-propyl 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, as well as branched saturated hydrocarbon groups of 6 carbon atoms. Suitable aryl groups are exemplified by, but not limited to, phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethyl phenyl. Suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl groups. Suitable monovalent halogenated hydrocarbon groups include, but are not limited to, a halogenated alkyl group of 1 to 6 carbon atoms, or a halogenated aryl group of 6 to 10 carbon atoms. Suitable halogenated alkyl groups are exemplified by, but not limited to, the alkyl groups described above where one or more hydrogen atoms is replaced with a halogen atom, such as F or Cl. For example, 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 are examples of suitable halogenated alkyl groups. Suitable halogenated aryl groups are exemplified by, but not limited to, the aryl groups described above where one or more hydrogen atoms is replaced with a halogen atom, such as F or Cl. For example, chloroaryl and fluoroaryl are suitable halogenated aryl groups.

[0036] In specific embodiments when at least one X and / or at least one Y is a hydrocarbyl group, the hydrocarbyl group is unsubstituted, and is selected from aliphatic hydrocarbon groups and aromatic hydrocarbyl groups. In more specific embodiments, the hydrocarbyl group is selected from alkyl groups and aryl groups.

[0037] Examples of suitable alkyl groups for X, Y, and R^ include methyl, ethyl, propyl (e.g. iso-propyl 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, hexadecyl, and octadecyl, as well as branched saturated hydrocarbon groups having from 6 to 8 carbon atoms. Examples of suitable non-conjugated cyclic groups (e.g. cycloalkyl groups) include cyclobutyl, cyclohexyl, and cycloheptyl groups.

[0038] In certain embodiments, each R^ independently has from 1 to 8, alternatively from1 to 7, alternatively from 1 to 6, alternatively from 1 to 5, alternatively from 1 to 4, alternatively from 1 to 3, alternatively from 1 to 2, alternatively 1, carbon atoms.

[0039] In one embodiment, subscript a is 10. In another embodiment, subscript a is 12. In one embodiment when subscript a is 10, at least one, alternatively at least two, alternatively at least three, alternatively at least four, alternatively at least five, alternatively at least six, alternatively at least seven, alternatively at least eight, alternatively at least nine, alternatively all 10 of X and Y as indicated by subscripts b and c, respectively, are halogen atoms. In one embodiment when subscript a is 12, at least one, alternatively at least two, alternatively at least three, alternatively at least four, alternatively at least five, alternatively at least six, alternatively at least seven, alternatively at least eight, alternatively at least nine, alternatively at least 10, alternatively at least 11, alternatively all 12 of X and Y as indicated by subscripts b and c, respectively, are halogen atoms.

[0040] Typically, the two cations of the salt of the catalyst (B) are independently selected Brønsted or Lewis acids. In one embodiment, each of the two cations of the catalyst (B) are independently selected Brønsted acids. In another embodiment, each of the two cations of the catalyst (B) are independently selected Lewis acids. In yet another embodiment, one cation is a Brensted acid, and the other is a Lewis acid.

[0041] In one embodiment, at least one cation comprises, alternatively both cations comprise, an independently selected Brønsted acid. When at least one cation comprises a Brønsted acid, the cation may comprise or be a proton (H+), which may optionally be associated with a molecule. For example, in one embodiment, at least one cation comprises, alternatively both cations comprise, a proton associated with a molecule having the general formula Z-O-Z, where each Z is independently selected from H, a silyl group, an arene, and a substituted or unsubstituted hydrocarbyl group, which may also include one or more heteroatoms other than or in addition to O. Alternatively, the molecule may be a silane compound or a hydrocarbon.

[0042] In specific embodiments when at least one cation comprises, alternatively both cations comprise, a proton associated with a hydrocarbon, the hydrocarbon comprises at least one unsaturated moiety, which may be aliphatic or aromatic. For example, when the hydrocarbon comprises at least one unsaturated moiety, the hydrocarbon may be an alkene, an alkyne, an arene, etc.

[0043] Suitable hydrocarbyl groups Z include any of those described above for X and Y.

[0044] As introduced above, each Z may independently include a heteroatom in the chain other than carbon. In such embodiments, Z may be considered a heterocarbyl group. Suitable heterocarbyl groups include any of the hydrocarbyl groups described above, but including one or more heteroatoms, such as oxygen, sulfur, nitrogen, etc. Depending on a selection of Z in such embodiments, the molecule may be a glycol ether or derivative thereof.

[0045] Silyl groups are known in the art and comprise at least one silicon atom. When Zis a silyl group, typically a silicon atom of the silyl group is bonded to oxygen in the molecule. The silyl group may be, for example, a triorganosilyl group, e.g. (CH3)3Si-. Alternatively, the silyl group may comprise more than one silicon atom. For example, the silyl group may be a siloxy group.

[0046] When Z is the silyl group or the substituted or unsubstituted hydrocarbyl group, each Z may be linked together such that the molecule represented by the general formula Z-O-Z is cyclic or a ring structure. As but one example, the molecule represented by the general formula Z-O-Z can be tetrahydrofuran (THF). In such embodiments, each Z can be considered a C2 hydrocarbon moiety linked together (or one Z can be a C1 hydrocarbon moiety and the other Z can be a C3 hydrocarbon moiety linked together, as the total number of carbon atoms linked together in such an embodiment would be four).

[0047] In another embodiment, at least one cation comprises, alternatively both cations comprise, a proton associated with a hydrocarbon and / or a silane compound. Specific examples of suitable hydrocarbons include those described above for Z, but in the form of hydrocarbon molecules rather than hydrocarbon substituents (i.e., not in monovalent form). By way of example, a hexenyl group described above for Z would be suitable as the hydrocarbon as the molecule as hexene, i.e., not in monovalent form.

[0048] In specific embodiments when at least one cation comprises, alternatively both cations comprise, a proton associated with a hydrocarbon, the hydrocarbon comprises at least one unsaturated moiety, which may be aliphatic or aromatic. For example, when the hydrocarbon comprises at least one unsaturated moiety, the hydrocarbon may be an alkene, an alkyne, an arene, etc. In one embodiment, the proton can be associated with arene to give an arenium cation. Other examples of molecules suitable for association with the proton when the cation comprises the proton include cyclic thioethers, nitriles, ketones, carboxylic acids, esters, amides, and combinations thereof.

[0049] In one embodiment, at least one cation comprises, alternatively both cations comprise, an independently selected Lewis acid.

[0050] In one embodiment, at least one cation comprises a Lewis acid, and the Lewis acid comprises a silylium cation or a carbocation.

[0051] In specific embodiments when at least one cation comprises a Lewis acid, and the Lewis acid comprises a silylium cation, the silylium cation has the formula (R4)3Si+, where each R4is independently selected from H, a substituted or unsubstituted hydrocarbyl group, and a halogen atom. Examples of substituted and unsubstituted hydrocarbyl groups as well as halogen atoms are described above. In specific embodiments, each R4is an independently selected alkyl group. In other embodiments, at least one R4is a halogen atom, and the remaining of R4are alkyl groups.

[0052] In further specific embodiments when at least one cation comprises a Lewis acid, and the Lewis acid comprises a silylium cation, the silylium cation is associated with a silane compound, a hydrocarbon, or a molecule having the general formula Z-O-Z, where each Z is independently selected and defined above. When the silylium cation is associated with a hydrocarbon, the hydrocarbon comprises at least one unsaturated moiety, which may be aliphatic or aromatic. For example, when the hydrocarbon comprises at least one unsaturated moiety, the hydrocarbon may be an alkene, an alkyne, an arene, etc.

[0053] Specific examples of suitable carbocations include areniums, benzyl, t-butyl, trityl, CH3+, and other tertiary hydrocarbon cations. One specific example of a suitable arenium is benzenium. One of skill in the art readily understands other suitable carbocations based on aromatic and aliphatic hydrocarbons.

[0054] The organosilicon component (A) and / or the catalyst (B) may also be disposed in a vehicle, e.g., a solvent which solubilizes the respective component, alternatively a vehicle which merely carries or disperses, but does not solubilize, the respective component. Such vehicles are known in the art. Alternatively, the organosilicon component (A) and / or the catalyst (B) may be combined neat. Further still, the organosilicon component (A) and the catalyst (B) may also be utilized neat but then may be combined with other components, e.g., a vehicle or solvent, when preparing the organosilicon compound with components (A) and (B).

[0055] Suitable vehicles include organic oils, organic solvents and mixtures of these.

[0056] Alternatively, the vehicle may comprise an organic solvent. Examples of organic solvents include: aromatic hydrocarbons, such as benzene, toluene, xylene, mesitylene, etc.; aliphatic hydrocarbons, such as heptane, hexane, octane, etcand other organic compounds that present as liquid / fluid at typical reaction temperatures, such as, white spirits, mineral spirits, naphtha, and the like, as well as derivatives, modifications, and combinations thereof.

[0057] The vehicle, if utilized, is different from components (A) and (B).

[0058] As introduced above, in various embodiments, the method comprises combining the organosilicon component (A) and a pre-catalyst (B1) different from the catalyst (B), and wherein the catalyst (B) is formed in situ in the presence of the organosilicon component (A) and the arene compound.

[0059] Exemplary examples of the pre-catalyst (B1) include (H)2[B12Cl12]·6(H2O), (H)2[B12Br12]·6(H2O), (H)2[B12H12]·6(H2O), (H)2[B12I12]·6(H2O), (H)2[B12CI11Br]-6(H2O), (H)2[B10Cl10]·6(H2O), (H)2[B10Br10]·6(H2O), (H)2[B12Cl11(OH)]·6(H2O), (H)2[B12F12]·6(H2O), (H)2[B12Cl9(OH)3]·6(H2O), H[Et3Si][B12Cl9(OH)3]·6(H2O), [Et3Si]2[B12Cl12], H[Et3Si][B12Br12], H[Et3Si][B12Cl12], [Et3Si]2[B12Br12], [Et3Si]2[B12I12], [Et3Si]2[B12Cl11Br], [Et3Si]2[B10Cl10], [Et3Si]2[B10Br10], [Et3Si]2[B12F12],[C6H712[B 12^H2]>H[C6H7][B12Cll2Lanclcombinations thereof. One of skill in the art readily appreciates how, in any of the exemplary examples above, any chlorine atom may be replaced with another halogen atom, and different combinations are contemplated in view of the selections of X and Y and subscripts a and b in the catalyst (B) and corresponding pre-catalyst (B1).

[0060] The exemplary examples of the pre-catalyst (B1 ) above include both hydrated (or “wet”) and non-hydrated (or “dry”) species. As described below, the number of water molecules shown is representative and may vary.

[0061] In specific embodiments, the pre-catalyst (B1) comprises the hydronium salt of a boron cluster (a dianionic boron cluster). As described above, as one exemplary example, the counterion to the dianionic boron cluster can simply be two protons (H+). The boron cluster is extremely stable, and non-coordinating. Because the boron cluster is substantially noncoordinating, the associated proton or counterion is strongly acidic. Because the proton or counterion is strongly acidic, the proton will interact very strongly with water molecules. Typically, the pre-catalyst (B1) in hydrated form cannot be completely dried to become free of water by traditional means (e.g. heating under vacuum). Generally, even after drying excess water under vacuum, from two to six or more water molecules may remain associated with the boron cluster. The representations below show the same exemplary species of the pre-catalyst that is hydrated in detailed representation form, ionic representation form, and simplified representation form. Without wishing to be bound by theory, it is to be understood that despite the representation, the negative charge is delocalized across the boron cluster and as such the proton and corresponding associated protons are also understood to be delocalized.Representation Representation"Detailed"Representation

[0062] In the method of the subject disclosure, either the hydrated or non-hydrated versions of the pre-catalyst (B1) may be utilized. The hydrated forms of the pre-catalyst (B1) can be converted to the dry or non-hydrated forms via the methods described herein. The hydrated forms of the pre-catalyst (B1) can be converted to the dry or non-hydrated forms via the methods described herein and in U. S. Provisional Patent Application No. 63 / 784,583 filed on 07 April 2025 which is incorporated by reference herein. Further still, the catalyst (B) can be formed in situ, orsynthesized prior to use, from other routes not reliant on the pre-catalyst (B1). In specific embodiments, the pre-catalyst (B1) is free of water molecules.

[0063] By way of example, because the cation, e.g. the proton, associated with the boron cluster is strongly acidic, the proton may react with a hydridic Si-H bond. The boron cluster will “dry” in-situ through reaction of the Si-H material with the acidic water, forming a by-product disiloxane. More specifically, the proton may react with a hydridic Si-H bond to make silylium and H2- TWO silyliums can then react with water to form a disiloxane, regenerating two protons. As the waters are subsequently removed, the proton becomes less stabilized by the coordination of water and thus becomes more acidic and thus more reactive. This reaction cascade continues until all the protons are reacted and the silylium remains as counterion. This is summarized below (where R in this particular instance is simply generic):Alternatively or in addition, the boron cluster can by “dried” in situ via a reaction with a chlorosilane, where silylium and HCI gas are prepared by drying rather than silylium and H2 gas.

[0064] Hence the hydrated or acidic form of the boron cluster can be converted to a silylium salt. In both the hydrated and silylium salt structures, the counterion is at most only very weakly coordinated to the boron cluster and these compounds should be seen as mostly ionic.

[0065] The catalyst (B), whether used discretely or formed in situ, comprises a halosilylium, typically a chlorosilylium. The halosilylium is cationic and associated with the boron cluster, which is anionic and is the counterion.

[0066] One exemplary example of the reaction mechanism for exchanging alkyl (e.g. methyl) and halogen (e.g. chlorine) is below (where Me indicates methylW] In this specific example, and the halosilylium species is [SiMe2CI]+as a result of the first organosilicon compound (A1) being Me2SiCl2, with one of skill in the art appreciatinghow different halosilylium species would result from different organosilicon compounds. The halosilylium facilitates the exchange of a methyl group to give MesSiCI via methyl group exchange. Since in theory such Me / CI transfer steps may be reversible and may differ depending on the composition of the first organosilicon compound (A1), one of skill in the art can appreciate how the composition of the first organosilicon compound (A1) can be modulated to obtain the desired target compound after methyl group / chlorine atom exchange. The extent of the reaction may be limited by thermodynamics, but can be driven by removal of either the reactants or products by means such as, but not limited to, distillation, etc.

[0068] Boron clusters are extremely stable, and will not be decomposed by the silylium. In addition, boron clusters are substantially non-coordinating, thus they do not significantly quench the Lewis acidity of the silylium cation. This key combination of a highly Lewis acidic “free” silylium cation and a highly stable anionic boron cluster is what makes catalytic activity of the catalyst (B) possible.

[0069] The catalyst (B) (or the pre-catalyst (B1)) is utilized in a catalytic amount. The catalytic amount can be readily determined by one of skill in the art. In certain embodiments, the catalytic amount of the catalyst (B) (or the pre-catalyst (B1)) is from greater than 0 to 10, alternatively from greater than 0 to 9, alternatively from greater than 0 to 8, alternatively from greater than 0 to 7, alternatively from greater than 0 to 6, alternatively from greater than 0 to 5, alternatively from greater than 0 to 4, alternatively from greater than 0 to 3, alternatively from greater than 0 to 2, alternatively from greater than 0 to 1, alternatively from greater than 0 to 0.9, alternatively from greater than 0 to 0.8, alternatively from greater than 0 to 0.7, alternatively from greater than 0 to 0.6, alternatively from 0 to 0.5, weight percent based on the total weight of the organosilicon component (A).

[0070] The target organosilicon compound is prepared via alkyl or halogen atom exchange. The reaction is typically carried out at an elevated temperature that is greater than room temperature. In certain embodiments, the elevated temperature is from greater than room temperature to 250, alternatively from 50 to 250, alternatively from 75 to 225, alternatively from 100 to 220, °C. In these or other embodiments, the reaction is carried out an elevated pressure greater than atmospheric pressure. In certain embodiments, the elevated pressure is from greater than atmospheric pressure to 5,000 kPa. The elevated pressure may be a function of gas generation from the reaction in a sealed reactor, vapor pressures of the reactants, intermediates, and products, the presence or absence of any optional vehicles, and / or inert gas pressure., etc.

[0071] The structure of the target organosilicon compound formed via the method is a function of the particular organosilicon component (A) utilized, including the species of the first organosilicon compound (A1) and the presence (and selection) or absence of the second organosilicon compound (A2). The target organosilicon compound is different from the compounds of the organosilicon component (A), including the first and second organosiliconcompounds (A1), (A2).

[0072] In certain embodiments, the target compound has the general formula Rx’Hy’Q4_ x’.y’Si, where each R is an independently selected alkyl group having from 1 to 4 carbon atoms, each Q is an independently selected halogen atom, 1<x’<3, 0<y’<2, and x’+y’ is from 1 to 4, with the proviso that the target compound is different from the first organosilicon compound (A1) and, if utilized, the second organosilicon compound (A2).

[0073] The target organosilicon compound is typically prepared in a reaction product. The reaction product may include the target organosilicon compound and other species of organosilicon compounds. For example, it is possible that there could be rearrangement of other silicon-bonded groups in certain byproducts produced along with the organosilicon compound, which are not the target species. These certain byproducts may be utilized for other purposes, recycled, etc. In fact, certain byproducts may be other than organosilicon compounds and instead be halosilanes, e.g. SiCl4- When byproducts other than organosilicon compounds are prepared via the method, the reaction product still includes organosilicon compounds. However, these other byproducts can also be desirable and advantageously prepared for their other end use applications.

[0074] In certain embodiments, the target organosilicon compound is free from silicon-bonded hydrogen atoms. In such embodiments, the target compound may have the general formula Rx’Q4.x’Si, where each R is an independently selected alkyl group having from 1 to 4 carbon atoms, each Q is an independently selected halogen atom, and 1^x’<3, with the proviso that the target compound is different from the first organosilicon compound (A1) and, if utilized, the second organosilicon compound (A2).

[0075] In certain embodiments, the method further comprises isolating the organosilicon compound from the reaction product.

[0076] The following examples, illustrating embodiments of this disclosure, are intended to illustrate and not to limit the invention. Unless otherwise noted, all reactions are carried out under air, and all solvents, substrates, and reagents are purchased or otherwise obtained from various commercial suppliers (e.g. Strem Chemicals, Acros Organics, Sigma-Aldrich, etc.) and utilized as received.

[0077] A brief summary is provided in T able 1 below, setting forth information as to certain abbreviations, shorthand notations, and components utilized in the Examples, as well as their sources. In the Tables below, “C.” prior to identification of each Component (B) indicates a Comparative Component (B).

[0078] In each of the Examples, the catalyst (B) is prepared in situ from a pre-catalyst. Thus, each component (B) is referred to below as a Pre-Catalyst, with the corresponding catalyst being prepared in situ in each Practical Example.

[0079] Table 1: Materials Utilized and SourcesSynthesis Examples

[0080] Synthesis Example 1: (H)2[B12Cli2]-6(H2O)

[0081] In a well-ventilated fume hood, to a 500 mL round-bottom flask was added CS2[B-|2H-|2] (4 g, 9.8 mmol) and deionized (DI) water (200 mL). The flask was fitted with a water-cooled condenser. The top of the condenser was open to the atmosphere. The mixture was heated to 70 °C with stirring (magnetic stirrer). At this temperature, the mixture was colorless and homogeneous. To the mixture was added trichloroisocyanuric acid (18.24 g, 78.5 mmol) in four portions over 48 h. During the reaction, a white crystalline solid precipitated. The progress of the reaction was monitored via 1 ^B NMR spectroscopy. When the reaction was complete, the suspension was allowed to cool to ambient temperature and left to stand for 18 h. The suspension filtered through a disposable glass frit into a 250 mL round-bottom flask. To the stirring filtrate was added a solution of triethylamine hydrochloride (5.41 g, 39.3 mmol) in water (10 mL). This resulted in the immediate precipitation of a copious quantity of white solid. The suspension was filtered through a disposable glass frit and the filter cake was washed on the frit with DI water. The filtrant was dried under vacuum at 50 °C. ^H, ^C, and ^B NMR spectroscopy confirmedthe identity of the isolated white solid as [Et3NH]2[B-| 2£=',121 (6.85 g, 9.0 mmol, 92%).

[0082] The [Et3NH]2[B-|2Cli21 was suspended in DI water (10 mL) at ambient temperature in a 50 mL round-bottom flask. With stirring, a solution of NaOH (50% in water, 1.5 mL) was added dropwise, and the suspension became a hazy homogeneous solution. The solution was filtered, and the filtrate was concentrated using a rotary evaporator to a volume of ca. 5 mL in a concentrated solution. To the concentrated solution was added DI water (10 mL) to give a diluted solution, and the diluted solution was again concentrated using a rotary evaporator to a volume of ca. 5 mL. The concentration step was repeated one more time to give a solution. To the solution was added a solution of cesium chloride (6.6 g, 39.2 mmol) resulting in the precipitation of a white crystalline solid in a suspension. The suspension was heated until the solid dissolved. White crystals precipitated upon cooling to ambient temperature. The crystalline solid was isolated via filtration and dried under vacuum at 80 °C. 5.91 g. ^H, ^C, andNMR spectroscopy confirmed the identity of the isolated white solid as Cs2[B-|2CI-|2] 73% yield.

[0083] A suspension of Cs2[B-|2CI-|21 (1 g) inD|water (10 mL) was stirred with prewashed (H+) ion exchange resin (10 g) for 10 minutes to give a solution. The solution was decanted and the resin was rinsed with two portions of DI water (2 x 10 mL). The combined solution / washings were concentrated on a rotary evaporator at 50 °C and then under high vacuum at 50 °C to give a pale tan powder. The target compound was isolated in quantitative yield.

[0084] Synthesis Example 2: [Et3Si]2[B-| 2CI -|?]

[0085] In an argon-filled glovebox, to (H)2[B-|2CI-|21'6(H2O) (165.7 mg, 0.25 mmol) in a 40 mL scintillation vial with no cap or stir bar was added in a single portion an excess of triethylsilane (1.45 g, 12.45 mmol, 50.0 equiv) along with toluene (1.0 mL). The reaction mixture was heated at 80 °C for 4 h resulting in vigorous evolution of gas. Once the bubbling had stopped and an oil phase had formed at the bottom of the reaction mixture, the vial was taken off the heating plate and allowed to cool to room temperature, then placed in a -35 °C freezer for 3 days. After this time, a white solid had precipitated. The white solid was filtered and washed with hexanes (3 x 3 mL) and the solid was dried under vacuum yielding 161 mg of a white powder (yield = 82%). A small amount of the solid (20 mg) was heated at 70 °C in benzene-d6 and the solution was analyzed by NMR spectroscopy, revealing the formation of [EtsSi CgDefelB 12CI12L

[0086] Synthesis Example 3: (H)2[B-|2Br-|2]’6(H2O)

[0087] In a 60 mL glass vial, (H+) ion exchange resin (10 g) was washed several times with 30 mL portions of DI water. To the washed resin, suspended in DI water (30 mL), was added Cs2[Bi2Hi21 (1 g, 2.45 mmol). The mixture was swirled periodically until all the Cs2[B-|2H-|21 had dissolved (ca. 30 minutes). The mixture was filtered, and the resin was washed on the fritwith a portion of DI water (30 mL). The filtrate was passed through a 0.45 pm PDVF syringe filter into a 250 mL round-bottom flask, and a further portion of DI water (40 mL) was added (total volume 100 mL). To the pale tan solution, with stirring, was added NaBr (7.56 g, 73.5 mmol, 30 equiv) followed by trichloroisocyanuric acid (3.42 g, 14.72 mmol, 6 equiv) and the flask was heated in an aluminum block (block temperature = 70 °C). The mixture, which became red-orange, was stirred for 42 h. An additional portion of trichloroisocyanuric acid (1.14 g, 4.91 mmol, 2 equiv) was added and the block temperature was raised to 100 °C. The mixture was stirred for 96 h. 11 B NMR showed clean conversion to a single species. The solution was allowed to cool to ambient temperature. To the stirring solution was added solid sodium sulfite (3.7 g, 25.34 mmol), causing immediate decolorization. The mixture was filtered. To the filtrate was added a solution of [EtsNHJCI (1.34 g, 9.81 mmol, 4 equiv) in DI water (10 mL). A white solid precipitated. The suspension was stirred gently for 10 minutes, and then filtered. The retentate was washed with DI water, and dried under vacuum. The results of analyses by ^H, ^C, and ^B NMR spectroscopy in acetone-d6, and by high-resolution mass spectrometry (HRMS), were consistent with [Et3NH]2[B12Br12].

[0088] To a suspension of [Et3NH]2[B-|2Bri2] (1.0 g, 0.773 mmol) in DI water (10 mL) was added a 50 wt% solution of sodium hydroxide in water (1.0 mL, 1.515 g, [0.76 g NaOH], 19.0 mmol) to give a mixture. To the mixture was added DI water (20 mL) and the mixture became a clear, homogeneous solution. The mixture was filtered through a 0.45 pm PVDF syringe filter. To the filtrate was added a solution of CsCI (521 mg, 3.10 mmol, 4 equiv) in DI water (5 mL). The clear, homogeneous solution was concentrated under reduced pressure at 50 °C to a volume of ca. 5 mL. At this point, white crystalline solid precipitated. To the suspension was added DI water (10 mL) and the suspension was concentrated under reduced pressure at 50 °C to a volume of ca. 5 mL. This dilution / concentration step was repeated a further two times. The suspension was filtered and the retentate was washed on the filter with cold water (5 mL) and dried under vacuum at 50 °C.

[0089] (H+) ion exchange resin (10 g) was suspended in 25 mL DI water over night. The water was decanted, and the resin was washed with DI water (3 x 10 mL portions) and resuspended in DI water (10 mL). To the suspension was added Cs2[B-|2Br12]anclthe mixture was swirled periodically over ca. 30 min. The mixture was decanted, and the resin was washed with DI water (10 mL). The decantate and washings were combined and passed through a 0.45 pm PVDF syringe filter to give a pale tan solution. The solution was concentrated under reduced pressure at 50 °C and then under high vacuum to give a pale tan powder in quantitative yield.1H and 11B NMR were consistent with (H)2[B-|2Br-|21’6(H2O).

[0090] Synthesis Example 4: [Et3Si]2[B-|2Br12]

[0091] In an argon-filled glovebox, to (H)2[B-|2Br-|2l‘6(H2O) (300 mg, 0.25 mmol, 1.0 equiv) in a 40 mL scintillation vial with no cap or stir bar was added in a single portion an excess of triethylsilane (1.17 g, 10.06 mmol, 40.0 equiv) along with toluene (2 mL) to give a reaction mixture. The reaction mixture was heated at 60 °C for 6 h. Once the bubbling had stopped and the solids had dissolved, the sample was allowed to cool to room temperature, then placed in a -35 °C freezer for 5 days. During this time a solid precipitated. The solids were filtered and washed with hexanes (3 x 3 mL) and dried under vacuum yielding 289 mg of an off-white powder (yield = 87%). A small amount of the solid (20 mg) was heated at 70 °C in benzene-d6 and the solution was analyzed by NMR spectroscopy, revealing the formation of [Et3Si C6D612[B-|2Bri2]-

[0092] Synthesis Example 5: (H)2[B12li2]'6(H2O)

[0093] A microwave vial was charged with Cs2[B-|2H-|2] (100 mg, 0.26 mmol), acetic acid (10 mL), and iodine (2.11 g, 8.31 mmol) and the vial was heated to 230 °C for 2.5 h to give a solution. The solution was then quenched with a solution of Na2SO3 (1.8 g) in DI water (50 mL). The mixture was filtered through celite and to the filtrate was added solid [EtsNHJCI (79 mg, 0.572 mmol), resulting in the precipitation of solid. A small amount of this compound was taken up in aceton itrile / water and stirred vigorously with (H+) ion exchange resin for 2 h. 1H and NMR spectra were consistent with the formation of (H)2[B-|2H2]'6(H2O).

[0094] Synthesis Example 6: [Et3Si]2[B-|2H2]

[0095] In an argon-filled glovebox, to (H)2[B-|2ll2]’6(H2O) (303 mg, 0.17 mmol, 1.0 equiv) in a 40 mL scintillation vial with no cap or stir bar was added in a single portion triethylsilane (400 mg, 3.44 mmol, 30.0 equiv) and benzene (2 mL) to give a reaction mixture. The reaction mixture was placed on a heating block at 60 °C. At this point the solids were insoluble and the reaction mixture had a pinkish tint. After about 5 min, gas evolution was noted, and the reaction mixture was left at that temperature. As the bubbling intensified, the solid appeared to be white and the solution was colorless. After 1 h at 60 °C, the reaction mixture was heated to 80 °C and held at that temperature for 1 h. After this time, no further gas evolution was noted. Toluene (2 mL) was added to the reaction mixture and it was heated to 100 °C and held at that temperature for 1 h. The supernatant was removed and the solids were dried under vacuum yielding 270 mg (0.143 mmol, 84% yield) of [Et3Si]2[B-| 2112]as atan solid.

[0096] Synthesis Example 7: (H)2[B12CI11 Br] 6(H2O)

[0097] A 250 mL flask was charged with DI water (150 mL) and Cs2[B-|2H-|2] (6 g, 13.6 mmol) to give a mixture. The mixture was heated until all the components dissolved. Then, [NBu^Br (9.25 g, 28.7 mmol) was added, resulting in a white precipitate. This was vigorouslystirred for 3 h, after which the solid was washed extensively with water and dried under vacuum overnight, affording 8.35 g (NBu^tB-^H-^]- Of this material, 4 g (6.38 mmol) was added to a 100 mL round-bottom flask charged with acetonitrile (20 mL) which was cooled to -15 °C (ethylene glycol / CO2). To the cooled solution was added a solution of A / -bromosuccinimide (1.14 g, 6.38 mmol) in acetonitrile (10 mL) dropwise over 10 minutes and the mixture was stirred for 1 h at -15°C then overnight at room temperature. The mixture was then dried, extracted with CH2CI2, and the extracts were washed with three portions of water, dried over Na2SO4 and filtered. The filtrate was dried to give 4.069 g (NBU4)2[B-|2HI 1 Br], with a minor impurity that could not be removed (88%). 2.77 g of this material (3.92 mmol) was dissolved in MeOH (20 mL) and to the solution was added Na[BPh4] (2.69 g, 7.85 mmol), resulting in the precipitation of [NBu4][BPh4] as a white solid. The mixture was stirred for 1 h, then filtered and dried under vacuum. The filtrate was dried under vacuum and the resulting residue was suspended in H2O (25 mL). Concentrated HCI (25 mL) was then added. Then, A solution of NaOCI in water (~5%, 128mL, 86.2 mmol) was added dropwise and the mixture was heated at the reflux temperature overnight. HRMS and ^B NMR spectroscopy showed conversion to the desired product. The solution was cooled to room temperature and to the solution was added [EtsNHJCI (1.19 g, 8.64 mmol, 2.2 equiv), affording a white suspension. The suspension was stirred for 10 minutes then filtered and washed with water. The solid was washed into a separate flask with MeOH and to the solution was added (H+) ion exchange resin (3 g). The mixture was stirred slowly overnight. The solution gradually acquired a yellowish tint. The (H+) ion exchange resin was removed by filtration and the solution was concentrated to dryness under vacuum. 1.86 g of material was recovered. ”*H NMR analysis showed residual [HNEtsJ. The material was redissolved in MeOH and to the solution was added (H+) ion exchange resin (6 g) and allowed to stand overnight. The mixture was again filtered and dried to give a tan solid that was free from residual [EtsNH] as determined by NMR spectroscopy. (H)2[B-|2Cli2Br]‘6(H2O), 1.56 g, 62%).

[0098] Synthesis Example 8: [Et3Si]2[B-|2CI-| 1 Br]

[0099] In an argon-filled glovebox, to (H)2[B-|2ClnBr]-6(H2O) (400 mg, 0.56 mmol, 1.0 equiv) in a 40 mL scintillation vial with no cap or stir bar was added in a single portion triethylsilane (1.3 g, 11.27 mmol, 20.0 equiv) and toluene (5 mL) to give a reaction mixture. The reaction mixture was heated at 50 °C for 1 h, and vigorous bubbling was observed. The vial was removed from the heat and allowed to react at room temperature for 2 h. After ca. 2 h, bubbling had subsided, and an separate phase had formed at the bottom of the vial. The sample was placed on a heating plate at 100 °C for 15 min, and then allowed to stand at room temperature for 4 days. During this time a brownish solid had formed. The supernatant was removed, and the solidwas stirred with heptane at room temperature for 24 h. The heptane was removed, and the solid was dried, yielding [Et3Si]2[B12Cl11Br] (390 mg, 84% yield). A small amount of the solid (20 mg) was heated at 70 °C in benzene-d6 and the solution was analyzed by NMR spectroscopy, revealing the formation of [Et3Si·C6D6]2[B12Cl11Br]. A small amount of the solid (20 mg) was also fully dissolved in 80 °C benzene, and allowed to cool to room temperature, leading to growth of crystals of [Et3Si]2[B12Cl11Br] that were suitable for single-crystal X-ray diffraction.

[0100] Synthesis Example 9:(H)2[B10Cl10]·6(H2O)

[0101] To a solution of Na2[B10H10] (2 g, 12.2 mmol) in H2O (20 mL) was added concentrated HCI (10 mL). With stirring, a solution of NaOCI in water (6%, 302 mL, 243 mmol) was added to give a mxiture. The mixture was heated at the reflux temperature overnight. 1H and 11 B NMR spectra of the solution were consistent with the perchlorination of the cage.

[0102] To the crude reaction solution was added [EtsNHJCI (3.69 g, 26.8 mmol, 2.2 equiv) with stirring. White precipitate was observed immediately and was isolated by filtration. The wet solid was dissolved in MeOH and washed into a round-bottom flask that contained (H+) ion exchange resin (30 g) that had been washed three times with water. The mixture was allowed to stand overnight. The mixture was filtered to remove the ion exchange resin, and to the filtrate was added a solution of CsOH in water (50 wt%, 14.6 g, 48.8 mmol, 4 equiv). White precipitate formed and the mixture was stirred overnight. The solid was isolated by filtration and the filtrate was retained. Analysis of the solid by 1H NMR spectroscopy showed that residual [EtsNH] was present and so the solid was taken up in 1:1 H2O / CH3CN and to the solution was added (H+) ion exchange resin. Analysis by 1H NMR spectroscopy showed no residual [EtsNH] and so the solution was filtered and dried in vacuo affording 2.04 g of (H)2[B10Cl10]·6(H2O). The retained filtrate was free from [EtaNH] but was treated with (H+) ion exchange resin to ensure the complete removal of residual cesium cations. After standing overnight, the mixture was filtered and the water was removed under vacuum to give a further 2.74 g of (H)2[B10Cl10]·6(H2O) as a hygroscopic brownish solid. Total mass of 4.78 g (68%).

[0103] Synthesis Example 10: [Et3Si]2[B10Cl10]

[0104] In an argon-filled glovebox, (H)2[B10Cl10]·6(H2O) (325 mg, 0.57 mmol, 1.0 equiv) was loaded into a 30 mL vial, followed by toluene (9.9 g). Triethylsilane (2.45 g, 21.1 mmol, 37.0 equiv) was added, and the vial was placed on a hot plate (no stir bar, no cap). No bubbling was observed. The temperature was slowly increased to 100 °C while monitoring the mixture for gas generation. After 2 hours, the vial was removed from the heating block. The hot solution was added by pipette to another vial loaded with heptane (9.0 g). Immediately the mixture turned cloudy white. It slowly became more translucent, and white crystals started forming. The mixturewas left overnight to cool. Liquid was siphoned from the vial via pipette and the solid was dried under vacuum. White crystalline solid remained. The target [Et3Si]2[B-| QCI-I Q] was obtained as a white crystalline solid (312 mg, 79% yield). A small amount of the solid (20 mg) was heated at 70 °C in benzene-d6 and the solution was analyzed by NMR spectroscopy, revealing the formation of [Et3Si·C6D6]2[B10Cl10]- Synthesis Example 11: (H)2[B-|oBr-|o] ‘6(1^0)

[0105] To a solution of Na2[B10H10](2 g, 12.2 mmol) in H2O (20 mL) was added concentrated HBr (48%, 10 mL) and NaBr (12.5 g, 121.5 mmol, 10 equiv). With stirring, a solution of NaOCI in water (6%, 180 mL, 145 mmol) was added to give a mixture. The mixture was heated at the reflux temperature for 3 h after which HRMS confirmed the completion of the reaction. The mixture was cooled and to the mixture was added [EtsNHJCI (3.69 g), resulting in the formation of a white solid. This was isolated by filtration and dissolved in methanol and transferred to a flask that contained 40 g of (H+) ion exchange resin that had been washed three times with water. The mixture was allowed to stand overnight. Analysis via NMR spectroscopy indicated that there was residual [EtsNH], The solution was treated with a slight molar excess of CsOH, which produced a white solid. This was isolated by filtration. Both the solid and filtrate were separately treated with washed (H+) ion exchange resin in water and were allowed to stand overnight. The solutions, separately, were filtered and dried under vacuum to afford (H)2[B-|oBr-|o] ’6(H20) as a light brown solid. (9.58 g total, 77%).

[0106] Synthesis Example 12: [Et3Si]2[B10Br10]

[0107] In an argon-filled glovebox, (H)2[B10Br10]·6(H2O) (330 mg, 0.32 mmol, 1.0 equiv ) was loaded into a 40 mL scintillation vial with no stir bar and no cap, followed by toluene (8.6 mL). Triethylsilane (1.12 g, 9.6 mmol, 30 equiv) was added, and the vial placed on a hot plate. No bubbling was observed. The temperature was slowly increased up to 100 °C while monitoring the mixture for gas generation. After 3 hours, the vial was removed from the heating block. The hot solution was added by pipette to another vial loaded with 60 °C heptane (8.7 g). Immediately the mixture turned cloudy white. It slowly became more translucent, and white crystals began to form. The mixture was left overnight to cool. The supernatant was decanted from the vial via pipette and the solid dried under vacuum. The target [Et3Si]2[B10Br10]wasobtained as a white crystalline solid (282 mg, 77% yield).

[0108] Synthesis Example 13: (H)2[B12Cl11(OH)]·6(H2O)

[0109] Cs2[B12H12] (6.0 g, 15.0 mmol) and stir bar were added to a 500 mL roundbottom flask and the flask was placed into an ice bath. With vigorous stirring, dilute sulfuric acid was added dropwise using an addition funnel (120.0 mL, 38% v / v) to form a mixture. The mixture was heated at 90 °C for 5 h. Conversion to [B12H11(OH)]2− was confirmed by 11B NMRspectroscopy. The reaction mixture was then allowed to cool to room temperature and a solution of NaOCI in water (120.0 mL, 6%) was slowly added to the flask via an addition funnel while the contents were stirred vigorously. The reaction mixture was then stirred at room temperature for 2 h. The addition funnel was then replaced by a reflux condenser and the reaction was heated at 60 °C for 24 h. An additional portion of NaOCI solution (40 mL) was added and the temperature was increased to 100 °C. The reaction was monitored via HRMS.

[0110] Upon the completion of the reaction, the mixture was allowed to cool and was quenched with sodium sulfite until all yellow color dissipated. The solution was then concentrated under vacuum to give a white residue, which was recrystallized from hot water, giving 7.4 g of a white crystalline solid. The 11B NMR spectra were consistent with the [B12Cl11(OH)]2− dianion with a low concentration of an impurity.

[0111] A portion of the solid (550 mg) was then suspended in a mixture of water and (H+)ion exchange resin (2 g) that had been washed with water. The mixture was allowed to stand overnight. The resin was removed by filtration, and the filtrate was concentrated under vacuum to afford the desired (H)2[B12Cl11(OH)]·6(H2O) product as a white solid (385 mg, 98%).

[0112] Synthesis Example 14: [Et3Si]2[B12F12]

[0113] A solution of (H)2[B12F12] (48-52% in water) (5 g) was concentrated under vacuum (15 mbar) at 60 °C to give a clear solution. Upon cooling, the clear solution became a white crystalline mass. The solid was heated under high vacuum first at 60 °C for 30 min, and then at 120 °C for 2 h to give (H)2[B12F12]’6(H2O). Inanargon filled glovebox, to 388 mg of the (H)2[B12F12]·6(H2O) (0.83 mmol, 1.0 equiv) in a 40 mL scintillation vial with no stir bar and no cap was added in a single portion triethylsilane (1.9 g, 16.6 mmol, 20.0 equiv) and benzene (5 mL). The evolution of gas was immediately observed. The reaction mixture was heated to 60 °C, and allowed to stand at that temperature for 1 h. During this time, rapid evolution of gas was observed. The reaction was allowed to stand at 60 °C for 5 h, after which time the evolution of gas had stopped and a colorless oily layer had formed at the bottom of the vial. Heptane (0.7 mL) was added in a single portion to the mixture, and the mixture was allowed to stand at room temperature for 5 days. The product crystallized as colorless needles. The supernatant was removed, the solids were washed with heptane (2 x 2 mL) and then dried under vacuum, yielding 430 mg of a white crystalline solid (88% yield). A small amount of the solid (20 mg) was heated at 70 °C in benzene-dg and the solution was analyzed by NMR spectroscopy, revealing the formation of [Et3Si·C6D6]2[B12F12]-

[0114] Synthesis Example 15: [C6H7]2[B12Cl12]

[0115] To a stirred suspension of [Et3Si]2[B12Cl12] (as prepared in Synthesis Example 2) (307.9 mg, 0.392 mmol) in benzene (3 mL) in a 20 mL glass vial was addedtrifluoromethanesulfonic acid (139 pL, 235 mg, 1.57 mmol, 4 equiv) to give a mixture, and the mixture was stirred vigorously for 30 minutes to give a suspension. The suspension was a fine yellow solid in colorless supernatant which was concentrated under vacuum to ca. 1 mL to give a concentrate. To the concentrate was added pentane (5 mL) to give a mixture, and the mixture was briefly stirred, resulting in a supernatant. The supernatant was carefully decanted. This process was repeated with a further two portions of pentane (2 x 2.5 mL), resulting in a solid. The solid was dried under vacuum to give a white solid. NMR spectra were consistent with the formula [C6H7]2[B12Cl12].

[0116] Synthesis Example 16: (H)2[B12Clg(OH)3]-6(H2O)

[0117] A500 mL flask with a stir bar was charged with Cs2[B12H12] (6 g, 15 mmol). The flask was cooled in an ice bath and aqueous H2SO4 (53% v / v, 120 mL) was added dropwise with vigorous stirring to give a white suspension. The flask was removed from the ice bath and a reflux condenser was affixed. The mixture was heated at 100 °C for 20 h. 11B NMR showed conversion to the [B12(OH)3H9] dianion. The solution was cooled to room temperature. A solution of NaOCI in water (10-15%, 60 mL) was added dropwise via an addition funnel over ca. 20 min. The reflux condenser was reattached and the solution was heated at 60 °C for 24 h. The reaction was monitored via 11 B NMR spectroscopy. A further volume of NaOCI solution (20 mL) was added and the mixture was heated at 85 °C for 24 h. To the cooled solution was added [NBu4]Br (10.4 g) resulting in the precipitation of a white solid. The mixture was stirred for 1 h and then filtered. The isolated solid was recrystallized from boiling ethanol. A further crop of crystals was obtained by placing the mother liquor in the freezer overnight. NMR spectra were consistent with [NBu4][B12Cl9(OH)3]. Total mass 11.02 g, 75%.

[0118] To a solution of [NBu4][B12Cl9(OH)3] (1 g, 1.02 mmol) in acetonitrile (10 mL) in a 40 mL vial was added hexamethyldisilazane (745 pL, 3.55 mmol, 3.5 equiv). The mixture was stirred at 70 °C overnight. 11B NMR showed full conversion to the [B12Cl9(OSiMe3)3] dianion.

[0119] [NBu4]2[B12Cl9(OSiMe3)3] (818 mg, 0.681 mmol) was dissolved in MeOH (10 mL). A solution of Na[BPh4] (466 mg, 1.36 mmol, 2 equiv) was added, resulting in the precipitation of a white solid. After 1 h, the solution was filtered and the filtrate was concentrated to dryness. The residue was dissolved in MeOH / H2O, and to the solution was added (H+) ion exchange resin. The mixture was stirred overnight. 1H NMR spectroscopy showed the removal of the SiMe3 groups. The filtrate was dried in vacuo to give (H)2[B12Cl9(OH)3]·6(H2O) as a tannish solid (357 mg).

[0120] Synthesis Example 17: (H)2[B12H12] 6(H2O)

[0121] A 30 wt.% solution of (H)2[B12H12] in water was concentrated under vacuum at30 °C to give a deliquescent white solid (H)2[B-|2H-|2]‘6(H2O).Practical Examples:

[0122] General Procedure 1 for Examples 1-17 and Comparative Examples 1-2:CatalystMe3SiCI + MeSiCI3- ► Me4Si + Me2SiCI22h, 120 °C2h, 150 °C2h, 180 °C

[0123] In a nitrogen filled glovebox, each species of Pre-Catalyst as prepared or obtained above and identified below (=30mg) was weighed in a glass vial and transferred to a stainless steel reactor. The reactants (defined below) were weighed in a glass vial, and the pre-catalyst-containing vial was rinsed with the reactants and this mixture was also added to the stainless steel reactor. Table 2 below shows the amount of each Pre-Catalyst and reactant utilized in Examples 1-14 and Comparative Examples 1-3. In Table 2 below, Example 1 uses Pre-Catalyst (B1), Example 2 uses Pre-Catalyst (B2), and so on. Similarly, Comparative Example 1 uses PreCatalyst C.(B1), etc. C. E. indicates Comparative Example.

[0124] The reactor was sealed, and placed on an aluminum heating block. The reaction mixture was warmed up to 120 °C, and left to react at that temperature for 2 hours after which time heat was turned off and the sample was cooled to room temperature naturally. An aliquot (0.1 g) of this sample was dissolved in C6D6 (0.8 g) and analyzed by multinuclear NMR spectroscopy (1H, 29Si). The remainder of the reaction mixture was warmed up to 150 °C, and left to react at that temperature for 2 hours after which time heat was turned off and the sample was cooled to room temperature naturally. An aliquot (0.1 g) of this sample was dissolved in C6D6 (0.8 g) and analyzed by multinuclear NMR spectroscopy (1H, 29Si). The remainder of the reaction mixture was warmed up to 180 °C, and left to react at that temperature for 2 hours after which time heat was turned off and the sample was cooled to room temperature naturally. An aliquot (0.1 g) of this sample was dissolved in C6D6 (0.8 g) and analyzed by multinuclear NMR spectroscopy (1H, 29Si). An aliquot from Comparative Example 1 was only taken at 180 °C, which showed no reaction, which also confirmed no reaction took place at either 120 °C or 150 °C (due to lesser reactivities at lower temperatures).

[0125] General Procedure 2: Comparative Example 3

[0126] General Procedure 2 was the same as General Procedure 1, with the only difference being that after the reaction mixture was first warmed to 120 °C and left to react at that temperature for 2 hours, and after cooling to room temperature, the remainder of the reaction mixture was warmed up to 220 °C and left to react at that temperature for 30 minutes after whichtime heat was turned off and the sample was cooled to room temperature naturally. Aliquots were sampled and analyzed after each step of cooling, as in General Procedure 1.

[0127] General Procedure 3: Comparative Example 4:

[0128] General Procedure 3 was the same as General Procedure 1, with the only difference being that the reaction mixture was first warmed to 180 °C and left to react at that temperature for 2 hours, and subsequently cooled to room temperature. An aliquot was sampled and analyzed after cooling, as in General Procedure 1.

[0129] Table 2: Examples 1-17 and Comparative Examples 1-4:

[0130] Table 3: Product distribution for each of Examples 1-17 and Comparative Examples 1-5 (yields in %, C. E. means “Comparative Example”).

[0131] General Procedure 4 for Examples 18-34 and Comparative Example 5-6:CatalystMeSiCl3——→ Me4Si + Me3SiCl + Me2SiCl22h, 120 °C2h, 150 °C2h, 180 °C

[0132] General Procedure 4 was the same as General Procedure 1, except only MeSiCl3 was utilized as a reactant, as shown above. Table 4 below shows the amount of each PreCatalyst and reactant utilized in Examples 18-34 and Comparative Example 5. Table 5 shows the corresponding yield of each product. An aliquot from Comparative Example 5 was only taken at 180 °C, which showed no reaction, which also confirmed no reaction took place at either 120 °C or 150 °C (due to lesser reactivities at lower temperatures).

[0133] General Procedure 5 for Comparative Example 7:

[0134] General Procedure 5 was the same as General Procedure 2, with the only difference being that after the reaction mixture was first warmed to 120 °C and left to react at that temperature for 2 hours, and after cooling to room temperature, the remainder of the reaction mixture was warmed up to 220 °C and left to react at that temperature for 30 minutes after which time heat was turned off and the sample was cooled to room temperature naturally. Aliquots were sampled and analyzed after each step of cooling, as in General Procedure 1.

[0135] General Procedure 6: Comparative Example 8:

[0136] General Procedure 6 was the same as General Procedure 4, with the only difference being that the reaction mixture was first warmed to 180 °C and left to react at that temperature for 2 hours, and subsequently cooled to room temperature. An aliquot was sampled and analyzed after cooling, as in General Procedure 1.

[0137] Table 4: Examples 18-34 and Comparative Examples 5-8:

[0138] Table 5: Product distribution for Examples 18-34 and Comparative Examples 5-8 (yields in %).

[0139] General Procedure 7 for Examples 35-37 and Comparative Example 9:CatalystMe4SI + SICI42h, 120 °C2h, 160 °C2h, 180 °C

[0140] General Procedure 7 was the same as General Procedure 1, except Me4Si and SiCl4 were utilized as reactants, as shown above. Table 6 below shows the amount of each PreCatalyst and reactant utilized in Examples 35-37 and Comparative Example 9. Table 7 shows the corresponding yield of each product. C. E. once again indicates Comparative Example.

[0141] Table 6: Examples 35-37 and Comparative Example 9:

[0142] Table 7: Product distribution Examples 35-37 and Comparative Example 9: Inventive Examples (yields in %).

[0143] General Procedure 8 for Example 38:CatalystMe4Si + MeSiCl3→ Me3SiCl + Me2SiCl22h, 120 °C2h, 150 °C2h, 180 °C

[0144] General Procedure 8 was the same as General Procedure 1, except Me4Si and MeSiCl3 were utilized as reactants, as shown above. Table 8 below shows the amount of each Pre-Catalyst and reactant utilized in Example 38. Table 9 shows the corresponding yield of each product.

[0145] Table 8: Example 38:

[0146] Table 9: Product distribution for Example 38 (yields in %).

[0147] General Procedure 9 for Example 39-41 and Comparative Example 10:CatalystMe2SiCl2→ Me3SiCl + MeSiCl32h, 150 °C

[0148] General Procedure 9 was the same as General Procedure 1, except Me2SiCl2 was utilized as the reactant, as shown above. Table 10 below shows the amount of each PreCatalyst and reactant utilized in Examples 39-41 and Comparative Example 10. Table 11 shows the corresponding yield of each product. In Tables 11 and 12, C. E. indicates Comparative Example.

[0149] Table 10: Example 39-41 and Comparative Example 10:

[0150] Table 11: Product distribution for Comparative Examples 39-41 and Comparative Example 10 (yields in %).

[0151] The invention has been described in an illustrative manner, and it was to be understood that the terminology which has been used was intended to be in the nature of words of description rather than of limitation. Obviously, many modifications and variations of the present invention are possible in light of the above teachings. The invention may be practiced otherwise than as specifically described.

Claims

CLAIMSWhat is claimed is:

1. A method of preparing a target compound, said method comprising:combining (A) an organosilicon component and (B) a catalyst comprising a boron cluster to give a mixture; andpreparing a reaction mixture comprising the target compound from the mixture; wherein the organosilicon component (A) comprises (A1) a first organosilicon compound having at least one silicon-bonded C1-C4 alkyl group and optionally at least one silicon-bonded halogen atom, with the proviso that when the first organosilicon compound (A1) does not include a silicon-bonded halogen atom, the organosilicon component (A) further comprises a second organosilicon compound (A2) including at least one silicon-bonded halogen atom;wherein the target compound is different from the first organosilicon compound (A1) and, if utilized, the second organosilicon compound (A2); andwherein the catalyst (B) is capable of facilitating the exchange of one silicon-bonded alkyl group of a first silane molecule with a silicon-bonded halogen atom of a second silane molecule.

2. The method of claim 1, wherein the target compound has the general formula Rx’Hy’Q4_ x’.y’Si, where each R is an independently selected alkyl group having from 1 to 4 carbon atoms, each Q is an independently selected halogen atom, 1<x’<3, 0<y’<2, and x’+y’ is from 1 to 4.

3. The method of claim 1 or 2, wherein the first organosilicon compound (A1) has the general formula RxHyQzSi, where each R is an independently selected alkyl group having from 1 to 4 carbon atoms, each Q is an independently selected halogen atom, 1<x<3, 0<y<2, 1<z<3 and x+y+z=4.

4. The method of any one preceding claim, wherein the catalyst (B) comprises a salt comprising one dianion having a charge of -2 and two cations, wherein the one dianion comprises the boron cluster.

5. The method of claim 4, wherein the one dianion has the formula (BaX^Y^-, where subscript a is 10 or 12, subscripts b and c are each independently selected integers greater than zero and b+c=a, wherein X and Y may be the same or different, and each X and each Y is independently selected from halogen atoms, H, hydrocarbyl groups, -SiR^ groups, where each R1 is independently an alkyl group or a halogen atom, and -OR^ groups, where each R^is H or an independently selected alkyl group, methanesulfonyloxy (mesyloxy) groups, tosyloxy groups, triflyloxy groups, nitro-phenylsulfonyloxy (nosyloxy) groups, bromo-phenylsulfonyloxy (brosyloxy) groups, and 0C(0)R3 groups, where R^ is an alkyl group.

6. The method of claim 4 or 5, wherein the two cations of the salt of the catalyst (B) are independently selected Brsnsted or Lewis acids.

7. The method of claim 6, wherein at least one cation comprises a Brgsnsted acid, and wherein the cation comprises a proton, which may optionally be associated with a molecule.

8. The method of claim 7, wherein the cation comprises the proton, and wherein the proton is associated with a molecule having the general formula Z-O-Z, where each Z is independently selected from H, a silyl group, and a hydrocarbyl group.

9. The method of claim 6, wherein at least one cation comprises a Lewis acid.

10. The method of claim 9, wherein the Lewis acid comprises a silylium cation, a carbocation, or CH3+.

11. The method of claim 10, wherein the Lewis acid comprises the silylium cation; wherein the silylium cation has the formula (R^)3Si+, where each R^ is independently selected from H, a substituted or unsubstituted hydrocarbyl group, and a halogen atom; and wherein the silylium cation is optionally associated with a silane compound, a hydrocarbon, or a molecule having the general formula Z-O-Z, where each Z is independently selected from H, a silyl group, an arene, and a hydrocarbyl group.

12. The method of claim 11, where each R^ is an independently selected alkyl group.

13. The method of any one preceding claim, wherein the method comprises combining the organosilicon component (A) and a pre-catalyst (B1) different from the catalyst (B), and wherein the catalyst (B) is formed in situ in the presence of the organosilicon component (A).

14. The method of any one preceding claim, wherein: (i) the elevated temperature is from 100 to 220 °C.

15. The method of any one preceding claim, wherein: (i): the first organosilicon compound (A1) comprises Me4Si, MeSiCl3 or Me2SiCl2 where Me indicates methyl; or (ii) the organosilicon component (A) further comprises the second organosilicon compound (A2), wherein the second organosilicon compound (A2) comprises MeSiCIs, Me2SiCl2, or SiCl4, or (iii) the boron cluster comprises at least six halogen atoms; or (iv) any combination of (i) to (iii).

16. The method of any one of claims 1-13, wherein the first organosilicon compound (A1) comprises MeSiC^ or Me2SiCl2, where Me indicates methyl.

17. The method of any one of claims 1-13, wherein:(i) the first organosilicon compound (A1) consists essentially of MeSiCl3, where Me indicates methyl; or(ii) the first organosilicon compound (A1) consists essentially of Me2SiCl2; or(iii) the first organosilicon compound (A1) comprises MeSiCl3, and wherein the organosilicon component (A) further comprises the second organosilicon compound (A2), where the second organosilicon compound (A2) comprises Me2SiCl2; or(iv) the first organosilicon compound (A1) comprises Me4Si, and wherein the organosilicon component (A) further comprises the second organosilicon compound (A2), where the second organosilicon compound (A2) comprises MeSiCIs; or(v) the first organosilicon compound (A1) comprises MeSiCIs, and wherein the organosilicon component (A) further comprises the second organosilicon compound (A2), where the second organosilicon compound (A2) comprises MesSiCL18. The method of any one preceding claim, further comprising isolating the target compound from the reaction product.

19. The reaction product comprising the target compound prepared in accordance with the method of any one preceding claim.

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