Compositions and methods for reacting organosilicon compounds with silicon-based hydrides catalyzed by fluorinated arylborane Lewis acids

Abstract

The present invention provides compositions and methods that can be used to prepare various siloxanes. The compositions and methods employ fluorinated triarylborane Lewis acids, alkoxy-functional organosilicon compounds, and silicon-based hydrides. The fluorinated triarylborane Lewis acids catalyze the reaction of alkoxy moieties (from the organosilicon compound) and silicon-bound hydrogen atoms (from the silicon-based hydride) to form siloxane bonds.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application Serial No. 63 / 043,153, filed on June 24, 2020. U.S. Provisional Patent Application Serial No. 63 / 043,153 is hereby incorporated by reference. Technical Field

[0003] The composition comprises a hydrocarbyloxy-functional organosilicon compound, a silicon-based hydride, and a fluorinated triarylborane Lewis acid. In the process, the fluorinated triarylborane Lewis acid catalyzes the reaction of hydrocarbyloxy groups from the organosilicon compound with silicon-bound hydrogen atoms from the silicon-based hydride, thereby forming siloxane bonds in the resulting product. Background Art

[0004] The catalysts predominantly employed in the preparation of both siloxane intermediates and siloxane cured networks from Si-H functional silanes and siloxanes are platinum based catalysts. Due to the increasing cost of platinum (Pt) and other disadvantages such as yellowing of cured siloxane compositions or formation of black precipitates over time, there is a need in the industry for alternatives to Pt based catalysts. In addition, Pt based catalysts may also suffer from the disadvantage of requiring high temperatures (80°C - 110°C) to achieve sufficient reactivity to catalyze the formation of siloxane bonds. Summary of the invention

[0005] A composition comprises: A) a fluorinated triarylborane Lewis acid; B) a hydrocarbyloxy-functional organosilicon compound; and C) a silicon-based hydride. A method comprises combining starting materials comprising A) a fluorinated triarylborane, B) a hydrocarbyloxy-functional organosilicon compound, and C) a silicon-based hydride. DETAILED DESCRIPTION

[0006] The starting material A) in the compositions and methods described herein is a fluorinated triarylborane Lewis acid. The fluorinated triarylborane Lewis acid has the formula:

[0007] Each R o is an ortho substituent, each R m is a meta-substituent, and each R p is a para substituent, R L is optional and includes a functional group or a functional polymer group; and the subscript x is 0 or 1. In the above formula, R o1 To R o6 Each of R m1 To R m6 Each of the R p1 To R p3Each of R is independently selected from H, F or CF3; provided that: not all R o1-6 , R m1-6 and R p1-3 can all be H at the same time; not all R o1-6 , R m1-6 and R p1-3 can be F at the same time; and when R o1 To R o4 When two or more of them are CF3, then R o5 and R o6 are each independently selected from H or F. L is optional, i.e., when the subscript x=1, RL exists, and when the subscript x=0, R L Does not exist. L It may be a Lewis base that forms a complex with a fluorinated triarylborane Lewis acid and / or a molecule or moiety containing at least one electron pair that can be used to form a coordinate bond with a Lewis acid, and may be as described in paragraphs

[0024] to

[0025] of WO2019 / 055740 for R 4 R L Examples of include cyclic ethers such as tetrahydrofuran or tetrahydropyran. Alternatively, RL may be tetrahydrofuran (THF).

[0008] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 and R o6 Each of may be H. Alternatively, R o1 , R o2 , R o3 and R o4 Each of may be H. Alternatively, R o5 and R o6 Each of can be F.

[0009] Alternatively, R m1 , R m2 , R m3 , R m4 , R m5 and R m6 Each of may be CF3. Alternatively, R m1 , R m2 , R m3 and R m4 Each of may be CF3. Alternatively, R m5 and R m6 Each of may be F. Alternatively, R m5 and R m6 Each of can be H.

[0010] Alternatively, R p1 , R p2 and R p3 Each of may be H. Alternatively, R p1 and R p2 It can be H. Alternatively, R p3 It can be F. Alternatively, R p3 It can be CF3.

[0011] Alternatively, R o1 , R o2 , R o3 , R o4 , R o５ , R o6 , R p1 , R p2 and R p3 Each of may be H; and R m1 , R m2 , R m3 , R m4 , R m5 and R m6 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material A) may comprise tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct.

[0012] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R o6 , R m5 , R m6 , R p1 and R p2 Each of may be H; and R m1 , R m2 , R m3 , R m4 and R p3 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct.

[0013] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 and R p2 Each of can be H; R o５ , R o6and R p3 Each of may be F; and R m1 , R m2 , R m3 , R m4 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct.

[0014] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 , R p2 and R p3 Each of can be H; R o5 and R o6 can be F; and R m1 , R m2 , R m3 and R m4 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct.

[0015] Alternatively, R o1 , R o2 , R o3 , R o4 , R oS , R m6 , R p1 , R p2 and R p3 Each of may be H; and R m1 , R m2 , R m3 , R m4 , R m5 and R o6 Each of may be CF3. The subscript x may be 0. Alternatively, the starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane.

[0016] Alternatively, R m1 , R p1 , R o2 , R o3 , R o4 , R p2 , R p3 , R o5 and R m6 Each of may be H; and Ro1 , R m2 , R m3 , R m4 , R o6 and R m5 Each of may be CF3. The subscript x may be 0. Alternatively, the starting material A) may include (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane.

[0017] Alternatively, R o1 , R o2 , R o3 , R o4 , R p1 and R p2 Each of can be H; R o5 , R o6 , R m5 and R m6 Each of may be F; and R m1 , R m2 , R m3 , R m4 and R p3 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct.

[0018] Alternatively, the fluorinated triarylborane Lewis acid may be selected from the group consisting of: A1) tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct; A2) bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct; A3) bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct; A4) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-trifluorophenyl)borane A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane THF adduct; A6) bis(3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane; A7) bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct; and A8) a combination of two or more of A1) to A7). Alternatively, the starting material A) may be selected from the group consisting of: A1), A2), A3), A4), A5) and A7). Alternatively, the starting material A) may be selected from the group consisting of: A1), A2), A3), A4) and A5). Alternatively, the starting material A) may be selected from the group consisting of: A1), A2), A3), A4) and A5). Alternatively, the starting material A) may be selected from the group consisting of: A1), A2) and A7). Alternatively, the starting material A) may be selected from the group consisting of: A2) and A5). Alternatively, the starting material A) may be selected from the group consisting of: A2), A3), A4) and A5).

[0019] Fluorinated triarylborane Lewis acids are known in the art and can be prepared by known methods, such as those disclosed in WO2019 / 055740, in particular paragraphs

[0052] to

[0096] , by modifying appropriate starting materials.

[0020] The amount of starting material A) will depend on the type and amount of other starting materials used, however, based on the combined weight of starting materials A), B) and C) in the composition, starting material A) may be present in an amount of 0.1 ppm to 5 mol%, alternatively 0.1 ppm to 6000 ppm, alternatively 0.1 ppm to 600 ppm, alternatively 5 ppm to 6000 ppm, alternatively 5 ppm to 600 ppm, alternatively 5 ppm to 500 ppm, and alternatively 5 ppm to 100 ppm.

[0021] B) Organic silicon compounds

[0022] The starting material B) in the compositions and methods described herein is a hydrocarbyloxy-functional organosilicon compound, i.e., a compound having an average of at least one moiety of the formula -OR 2 An organosilicon compound containing a silicon-bonded group wherein each R 2is an independently selected monovalent hydrocarbon group having 1 to 6 carbon atoms. The starting material B) may be one organosilicon compound or a combination of two or more organosilicon compounds different from each other. 2 Examples of monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl (including n-propyl and isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl and isobutyl), pentyl and hexyl (including linear and branched isomers of 5 to 6 carbon atoms); and alkenyl groups such as vinyl, allyl, butenyl and hexenyl. Alternatively, each R 2 Alternatively, each R 2 It may be ethyl or methyl; alternatively methyl.

[0023] The starting material B) may include hydrocarbyloxysilane and / or organosiloxane oligomers or polymers. For example, the organosilicon compound may be B1) of formula R 1 (4-a) S O 2 a hydrocarbyloxysilane, wherein each R 1 independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, each R 2 is a monovalent hydrocarbon group having 1 to 6 carbon atoms as described above, and the subscript a is 1 to 4. 1 Examples of suitable monovalent hydrocarbon groups include, but are not limited to, those described above for R 2 The described alkyl groups include methyl, ethyl, propyl (including n-propyl and isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl and isobutyl), as well as pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, undecyl and octadecyl (and their branched isomers); cycloalkyl groups include cyclopentyl and cyclohexyl; alkenyl groups include vinyl, allyl, butenyl and hexenyl; and aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, 1-phenylethyl and 2-phenylethyl. 1 Examples of monovalent halogenated hydrocarbon groups of include, but are not limited to, chlorinated alkyl groups such as chloromethyl and chloropropyl groups; fluorinated alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, 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; chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl and 2,3-dichlorocyclopentyl; and fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-di-fluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl. Alternatively, each R 1can be a monovalent hydrocarbon group, alternatively an alkyl group or an aryl group. Alternatively, each R 1 It may be an alkyl group, such as an alkyl group having 1 to 6 carbon atoms. Alternatively, each R 1 It may be methyl or ethyl, alternatively methyl.

[0024] The starting material B1) may include alkoxysilanes, examples of which are: monoalkoxysilanes, such as trialkylalkoxysilanes; dialkoxysilanes, such as dialkyldialkoxysilanes; trialkoxysilanes, such as alkyltrialkoxysilanes; tetraalkoxysilanes; or combinations thereof. Examples of suitable monoalkoxysilanes include trimethylmethoxysilane (TMSOMe), trimethylethoxysilane, triethylethoxysilane, triethylmethoxysilane, vinyldimethylethoxysilane, allyldimethylmethoxysilane, vinyldimethylmethoxysilane, dimethylphenylmethoxysilane, methyldiphenylmethoxysilane, triphenylmethoxysilane, and combinations thereof. Examples of suitable dialkoxysilanes include diisobutyldiethoxysilane, n-octadecylmethyldiethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, di(4-tolyl)dimethoxysilane, and combinations thereof. Examples of suitable trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, p-tolyltrimethoxysilane, p-tolyltriethoxysilane, pentafluorophenyltriethoxysilane, 4-trifluoromethyltetrafluorophenyltriethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltrimethoxysilane, benzyltriethoxysilane, and combinations thereof. Examples of suitable tetraalkoxysilanes include tetraethoxysilane and tetra-n-propoxysilane. These alkoxysilanes are known in the art and can be prepared by known methods, such as alkoxylation of the corresponding chlorosilanes, and / or suitable alkoxysilanes are commercially available, for example, from Gelest, Inc. of Morrisville, Pennsylvania, USA.

[0025] Other commercially available alkoxysilanes include XIAMETER TM OFS-6070 Silane, XIAMETER TM OFS-6011 Silane, XIAMETER TM OFS-6020 Silane, XIAMETER TM OFS-6030 Silane, DOWSIL TM Z-6062 silane, DOWSIL TMZ-6300 silane, DOWSIL TM Z-6341 Silane, XIAMETER TM OFS-6040 Silane, DOWSIL TM Z-6023 silane, DOWSIL TM Z-6015 silane, XIAMETER TM OFS-6920 Silane, XIAMETER TM OFS-6690 Silane and XIAMETER TM OFS-6076 silane; all of which are commercially available from The Dow Chemical Company of Midland, Michigan, USA and / or its subsidiaries.

[0026] Alternatively, the starting material B) may include an organosiloxane oligomer or polymer. The organosiloxane oligomer or polymer may have the formula B2):

[0027] The hydrocarbyloxy functional group contained in the group, wherein each D independently represents an oxygen atom, a divalent hydrocarbon group, a divalent siloxane group or a combination of a divalent hydrocarbon group and a divalent siloxane group; each R X Independent expression -OR 2 A group in which each R 2 As mentioned above; each R 3 Independently selected from the above for R 1 The group consisting of the monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups described; subscript c represents 0, 1, 2 or 3; subscript e represents 0, 1 or 2; and subscript d has a value of 0 or greater, provided that the sum of (e+c) is at least 1, so that on average there is at least one R in the formula X Alternatively, the value of subscript d may have a value from 0 to 18. Alternatively, subscript c may be 1. Alternatively, subscript c may be 2 or 3. Alternatively, subscript e may be 0. Alternatively, subscript d may be 0. Alternatively, subscript d may be 2 to 5, alternatively 2 to 3.

[0028] Alternatively, each D may be independently selected from an oxygen atom and a divalent hydrocarbon group. Alternatively, each D may be an oxygen atom. Alternatively, each D may be a divalent hydrocarbon group, exemplified by an alkylene group such as ethylene, propylene, butylene or hexylene; an arylene group such as phenylene, or an alkylene aryl group such as:

[0029] Alternatively, one example of D may be an oxygen atom, while a different example of D is a divalent hydrocarbon group.

[0030] Alternatively, each RX may be independently selected from the group consisting of an alkoxy group and an alkenyloxy group.Alternatively, each X may be an alkoxy group, such as a methoxy group or an ethoxy group.

[0031] Alternatively, each R in the above formula 3 The alkyl groups may be independently selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

[0032] Alternatively, subscript b may be zero.

[0033] The organosiloxane oligomer or polymer may include the groups described by formula B2) above in an amount ranging from 0.2 mol% to 10 mol%, alternatively 0.5 mol% to 5 mol%, alternatively 0.5 mol% to 2.0 mol%, alternatively 0.5 mol% to 1.5 mol%, and alternatively 0.6 mol% to 1.2 mol% of the polymer.

[0034] The starting material B) may have a linear polyorganosiloxane backbone, i.e., a polydiorganosiloxane backbone. When the starting material B) has a polydiorganosiloxane backbone, the starting material B) may include an alkoxy-terminated polydiorganosiloxane, an alkoxysilylalkylene-terminated polydiorganosiloxane, or a combination thereof.

[0035] Alternatively, the starting material B) may comprise the formula B3):

[0036] A polydiorganosiloxane, wherein R 3 , RX and subscripts c, d and e are as described above, and subscript f has a value of 1 or greater. Alternatively, subscript f may have a value sufficient to provide the polydiorganosiloxane of formula B3) with a viscosity of at least 100 mPa·s at 25°C and / or a DP of at least 87. DP may be measured by GPC using polystyrene standard calibration. Alternatively, subscript f may have a value ranging from 1 to 200,000. Alternatively, in formula B3) above, each R3 may be selected from the group consisting of alkyl, alkenyl and aryl. Alternatively, for R 3 The alkyl group for R may be selected from the group consisting of methyl, ethyl and propyl. 3 The alkenyl group of R may be selected from the group consisting of vinyl, allyl and hexenyl. 3 The aryl group of can be phenyl. Alternatively, in the above unit formula, each R XIt may be a methoxy group or an ethoxy group. The organosiloxane oligomers and polymers of formula B3) may be prepared, for example, as described in U.S. Patent Application Publication No. 2020-0140618 or PCT Publication Nos. WO2019 / 005711 or WO2019 / 005713.

[0037] Alternatively, the organosiloxane oligomer or polymer may comprise the unit formula B4):

[0038] (R X R 3 2SiO 1 / 2 ) o (R 3 3SiO 1 / 2 ) p (R 3 2SiO 2 / 2 ) q (R X R 3 SiO 2 / 2 ) r (R X SiO 3 / 2 ) s (R3SiO 3 / 2 ) t (SiO 4 / 2 ) u , where R X Represents the above formula -OR 2 wherein the values ​​of the subscripts o, p, q, and r are such that o≥0, p≥0, q≥0, r≥0, s≥0, t≥0, u≥0, the amount (o+r+s) has an average value of 1 or more, alternatively 1 to 6, alternatively 1 to 3, and alternatively 1 to 2; and each R 3 Independently selected from the above for R 1 The group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups described. Alternatively, the amount (o+p+q+r+s+t+u) may be at least 3, alternatively 3 to 2000. Alternatively, the amount (q+r) may be 1 to 2,000, alternatively 1 to 50. Alternatively, the amount (o+p) may be 0 to 50, alternatively 0 to 2. Alternatively, 1≥s≥0. Alternatively, 1≥t≥0. Alternatively, the average value of the amount (o+r+s) is 1 to 6, alternatively 1 to 3, and alternatively 1 to 2. Alternatively, in the above unit formula B4), each R 3 can be selected from the group consisting of alkyl, alkenyl and aryl. 3 The alkyl group for R may be selected from the group consisting of methyl, ethyl and propyl. 3 The alkenyl group of R may be selected from the group consisting of vinyl, allyl and hexenyl. 3The aryl group of can be phenyl. Alternatively, in the above unit formula, each R X It may be methoxy or ethoxy.

[0039] Alternatively, (for example, when o has an average value of 2 and p=r=s=t=u=0), the starting material B) may comprise the formula B5):

[0040] R 3 2R X SiO-(R 3 2SiO) b -OSiR X R 3 2 polydiorganosiloxane, wherein each R 3 and each R X As described above, and subscript b ≥ 1. Alternatively, subscript b may be 1 to 2,000, alternatively 5 to 900, alternatively 5 to 50, and alternatively subscript b may be 1 to 50. Alternatively, in formula B5), each R 3 may be independently selected from the group consisting of alkyl (eg, methyl, ethyl and propyl), alkenyl (eg, vinyl, allyl and hexenyl) and aryl (eg, phenyl). Alternatively, in formula B5), each R X It may be methoxy or ethoxy. Polydiorganosiloxanes of formula B3), such as methoxy-terminated polydimethylsiloxane with a viscosity of 5 to 12 cSt, are commercially available from Gallester, and 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane is commercially available from Millipore Sigma of St. Louis, Missouri, USA.

[0041] Alternatively, the starting material B) may comprise the unit formula B6): (R 3 SiO 3 / 2 ) m (R 3 R X SiO 2 / 2 ) n (R 3 2R X SiO 1 / 2 ) z , where R 3 and R X As described above, and subscript m is >0 to 100, subscript n is 0 to 100, and subscript z is 0 to 20. Alternatively, subscript m may be >0 to 20, alternatively 1 to 20. Alternatively, subscript n may be 1 to 20. Alternatively, subscript z may be 0. Alternatively, subscript z may be >0 to 20. Alternatively, in unit formula B6), each R 3may be independently selected from the group consisting of: alkyl (e.g., methyl, ethyl, and propyl), alkenyl (e.g., vinyl, allyl, and hexenyl), aryl (e.g., phenyl), and halogenated alkyl (e.g., chloromethyl, chloropropyl, and trifluoropropyl). Alternatively, in unit formula B6), each R X It can be methoxy or ethoxy. Those skilled in the art will recognize that the alkoxy-functional siloxane resin can also include hydroxyl groups. Examples of suitable alkoxy-functional siloxane resins of formula B6) include DOWSIL 9000 from Dow Silicones Corporation of Midland, Michigan, USA. TM 3037、DOWSIL TM 3074、DOWSIL TM 1686、DOWSIL TM CF0189, DOWSIL TM Z-6289、DOWSIL TM US-CF2403 resin and DOWSIL TM 2405 resin.

[0042] Suitable resins for starting material B) and methods for their preparation are known in the art. For example, alkoxy-functional organopolysiloxane resins or resin-polymer blends prepared as described in U.S. Pat. No. 9,670,392; U.S. Pat. No. 10,125,225; or PCT Publication No. WO2014 / 124389 can be used as starting material B herein). Starting material B) can include one or more of the compounds described herein.

[0043] C) Silicon Hydride

[0044] The starting material C) in the compositions and methods described herein is a silicon-based hydride. The term "silicon-based hydride" means a molecule containing at least one silicon-bound hydrogen atom (SiH) per molecule. Alternatively, the silicon-based hydride may have more than one SiH per molecule. The silicon-based hydride used herein is capable of forming a siloxane bond in the presence of A) a fluorinated triarylborane Lewis acid and B) the above-mentioned organosilicon compound. The starting material C) may include a silicon-based hydride, or a combination of two or more silicon-based hydrides that are different from each other.

[0045] The silicon-based hydride can be a C1) silane (e.g., having one silicon atom per molecule). Alternatively, the silicon-based hydride can be oligomeric or polymeric. Polymeric silicon-based hydrides can be linear, branched, or resinous. For example, the silicon-based hydride can be a C2) polyorganohydrogensiloxane.

[0046] Cl) Silane

[0047] The starting material Cl) is of formula H k S i 5 (4-k) Silane, where each R 5 Independently selected from the above for R 1 The group consisting of the monovalent hydrocarbon group and the monovalent halogenated hydrocarbon group described, and the subscript k is 1 to 3, alternatively 1 or 2, and alternatively 1. Alternatively, each R 5 It may be an alkyl group, such as an alkyl group having 1 to 6 carbon atoms. Alternatively, each R 5 Alternatively, the starting material C1) may be of the formula HSiR 5 3 silane, wherein each R 5 is an alkyl group having 1 to 6 carbon atoms.

[0048] Examples of suitable silanes for starting material C1) are known in the art and are commercially available. Suitable silanes include triethylsilane, dimethylethylsilane, diethylmethylsilane, dimethylisopropylsilane, dimethyl-tert-butylsilane, triisopropylsilane, chloromethyldimethylsilane, tripropylsilane, tributylsilane, triisobutylsilane, trihexylsilane, trioctylsilane, cyclohexyldimethylsilane, dimethylphenylsilane, diphenylmethylsilane, triphenylsilane, phenylsilane, undecylbromosilane, 2-chloroethylsilane, dodecylsilane, n-octadecylsilane and (tridecafluoro-1,1,2,2-tetrahydrooctyl)silane, which are available from Sigma-Aldrich Inc. of St.Louis Missouri, USA or Gallester Inc. of Morrisville, Pennsylvania, USA.

[0049] C2) Polyorganohydrogensiloxane

[0050] When the starting material C2) polyorganohydrogensiloxane is used for the silicon-based hydride, the polyorganohydrogensiloxane may be a homopolymer or a copolymer. The polyorganohydrogensiloxane may be linear, branched or resinous. The silicon-bound hydrogen atoms in the polyorganohydrogensiloxane may be located at the terminal, the side group or at both the terminal and side group positions.

[0051] The polyorganohydrogensiloxane may include two or more siloxane units selected from: HR 4 2SiO 1 / 2 Unit, R 4 3SiO 1 / 2 Unit, HR 4 SiO 2 / 2 Unit, R4 2SiO 2 / 2 Unit, R 4 SiO 3 / 2 Unit, HSiO 3 / 2 Unit and SiO 4 / 2 Unit. In the above unit, each R 4 are independently selected monovalent hydrocarbon groups free of aliphatic unsaturation. 4 Examples of suitable monovalent hydrocarbon groups include, but are not limited to, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and their branched isomers); cycloalkyl groups such as cyclopentyl and cyclohexyl; and aryl groups such as phenyl, tolyl, xylyl, naphthyl, benzyl, 1-phenylethyl, and 2-phenylethyl. Alternatively, each R 4 It can be an alkyl group or a cycloalkyl group. 4 It may be an alkyl group such as methyl.

[0052] When the polyorganohydrogensiloxane is linear, that is, a polydiorganohydrogensiloxane, the polydiorganohydrogensiloxane may have a unit formula: (HR 4 2SiO 1 / 2 ) g (R 4 3SiO 1 / 2 ) h (R 4 2SiO 2 / 2 ) i (HR 4 SiO 2 / 2 ) j , where R 4 As described above, and the values ​​of the subscripts g, h, i and j are such that g≥0, h≥0, the amount (g+h)=2, i≥0, j≥0 and the amount (g+j)≥1, and the amount (i+j) can be from 0 to 1000.

[0053] Alternatively, the polydiorganohydrogensiloxane may have the formula where the subscript m is 0 or 1, and each R 6 Independently selected from H and R 4 The prerequisite is that each molecule has at least one R 6 It's a hydrogen atom.

[0054] Examples of suitable polyorganohydrogensiloxanes are:

[0055] i) pentamethyldisiloxane,

[0056] ii) bis(trimethylsiloxy)methyl-silane,

[0057] iii) tetramethyldisiloxane,

[0058] iv) bis-dimethylhydrogensiloxy-terminated polydimethylsiloxane,

[0059] v) bis-dimethylhydrogensiloxy terminated poly(dimethylsiloxane / methylhydrogensiloxane),

[0060] vi) bis-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane,

[0061] vii) bistrimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane),

[0062] viii) bistrimethylsiloxy-terminated polymethylhydrogensiloxane,

[0063] ix) Mainly composed of H(CH3)2SiO 1 / 2 Unit and SiO 4 / 2 The resin consists of units, and

[0064] x) a combination of two or more of i) to ix).

[0065] Methods for preparing linear and branched polyorganohydrogensiloxanes suitable for use as starting material C2) such as hydrolysis and condensation of organohalosilanes are well known in the art, as exemplified in U.S. Pat. Nos. 5,310,843; 4,370,358; 4,707,531; and 4,329,273. Polyorganohydrogensiloxanes are also commercially available, such as those available from Gallester Corporation under the following trade names: DMS-HM15, DMS-H03, DMS-H25, DMS-H31, and DMS-H41.

[0066] D) Solvent

[0067] Starting material D) is an optional solvent that can be used to promote the combination of starting materials A), B) and / or C) in the compositions and methods described herein. The solvent used herein is those that contribute to the fluidization of the starting material but do not react substantially with any of these starting materials. The solvent can be selected based on the solubility of the starting material and the volatility of the solvent. Solubility refers to that the solvent is sufficient to dissolve and / or disperse the starting material. Volatility refers to the vapor pressure of the solvent. For example, starting material A), fluorinated triaryl borane Lewis acid, can be dissolved in a solvent before step 1). Alternatively, starting material B) can be dissolved in a solvent before step 1), for example, when starting material B) is a viscous fluid, such as a gum, or is solid at room temperature, such as a resin. Alternatively, starting material C) can be dissolved in a solvent before step 1), for example, when starting material C) is a solid at room temperature, such as a resin. The solvent can be used in any amount, and the amount will be selected by those skilled in the art based on various factors, such as the selection of starting materials A), B) and C) and their solubility.

[0068] Suitable solvents may be hydrocarbons. Suitable hydrocarbons include aromatic hydrocarbons such as benzene, toluene or xylene; and / or aliphatic hydrocarbons such as heptane, hexane or octane. Alternatively, the solvent may be a halogenated hydrocarbon such as dichloromethane, 1,1,1-trichloroethane or methylene chloride. One solvent or a combination of two or more solvents may be used herein.

[0069] The amount of solvent may depend on a variety of factors, including the type of solvent selected and the amount and type of other starting materials selected. However, based on the combined weight of starting materials A), B) and C), the amount of solvent may be in the range of 0.1% to 99%, alternatively 2% to 50%.

[0070] method

[0071] The above method comprises: 1) combining starting materials including the above A) fluorinated triarylborane Lewis acid, B) organosilicon compound and C) silicon-based hydride. The starting material may optionally further include D) a solvent, which can be used to facilitate the combination of starting materials A), B) and C). For example, one or more of starting materials A), B) and C) can be dissolved in a solvent before mixing with starting material D). Alternatively, the starting material in step 1) can be essentially composed of the above starting materials A), B) and C) (and optionally D)). Alternatively, the starting material in step 1) can be composed of the above starting materials A), B) and C) (and optionally D)).

[0072] In making the starting material B) of the formula OR 2The starting materials are combined under conditions where the groups of the starting materials react with the silicon-bound hydrogen atoms of the starting materials C). The resulting products of step 1) include the reaction product of the starting materials B) and C) (which has a siloxane bond) and the starting materials C). 2 by-products. These conditions may include, for example, mixing by any convenient means. Conventional mixing equipment, such as a stirred batch reactor, may be used for mixing. Alternatively, when the alkoxy-functional organosilicon compound selected for the starting material B) and / or the silicon-based hydride selected for the starting material C) is viscous or solid (e.g., gum or resin), mixing under shear may be performed, for example, with an extruder. The composition may be formed, for example, by mixing the starting materials including A), B) and C) described above. The starting materials A), B) and C) may be combined at room temperature or lower, or may be heated. For example, when heated, a temperature of 50°C to 150°C, alternatively 100°C to 125°C may be used during mixing. Alternatively, in step 1), the temperature for combining the starting materials A), B) and C) (and D), when present) may be 5°C to 70°C. The starting materials A), B) and C) (and D), when present) may be combined simultaneously. Alternatively, starting materials A) and B) (and D), when present) can be combined to form a mixture, and thereafter, the mixture can be combined with starting material C) (and additional D), when present), for example by adding starting material C) (or a solvent solution thereof) to the mixture, for example by metering over a period of time or by adding in one or more aliquots.

[0073] The method may also optionally include one or more additional steps. The method may also include: step 2), during and / or after step 1), removing the formula HR generated during step 1) 2 Byproducts, and / or step 3), removing and / or neutralizing the residual fluorinated triarylborane Lewis acid in the product. Byproduct HR 2 Removal can be by any convenient means, such as stripping and / or burning. Removal and / or neutralization can be performed by adding E) a neutralizing agent to the product and optionally filtering the product afterwards. Steps 2) and 3) can be performed in any order. If particulate by-products are present, for example due to neutralization, the method may also include step 4) after neutralization, removing particles such as aluminum oxide by any convenient means such as filtering.

[0074] Starting material E) Neutralizing agent

[0075] Starting material E) is a neutralizing agent, which can be optionally used to neutralize starting material A in the product. Alumina, triphenylamine, triphenylphosphine, triethylamine and phenylacetylene are suitable neutralizing agents. Neutralizing agents are known in the art and can be commercially obtained, for example, from Millipore Sigma, St. Louis, Missouri, USA. The amount of neutralizing agent depends on various factors including the amount of starting material A), however, starting material E) can be present in an amount sufficient to provide a weight ratio of neutralizing agent to fluorinated triarylborane Lewis acid (E: A ratio) of 1: 100 to 1000: 1, alternatively 1: 1 to 1000: 1, and alternatively 1: 100 to 1: 1. Alternatively, when the neutralizing agent is triphenylphosphine or phenylacetylene, the E: A ratio can be 1: 1 to 20: 1. Alternatively, when the neutralizing agent is alumina, the E: A ratio can be 100: 1 to 1000: 1.

[0076] One or more of the above method steps may be carried out at a temperature of 5°C to 150°C, alternatively 5°C to 125°C, alternatively room temperature to 150°C, alternatively 5°C to 70°C, alternatively 5°C to 65°C, alternatively 10°C to 60°C, alternatively 15°C to 50°C, alternatively 20°C to 35°C, alternatively 5°C to 35°C, and alternatively room temperature. Alternatively, step 1) may be carried out at a temperature of 5°C to 70°C, alternatively 5°C to 65°C, alternatively 10°C to 60°C, alternatively 15°C to 50°C, alternatively 20°C to 35°C, alternatively 5°C to 30°C, and alternatively 30°C. Without being bound by theory, it is believed that performing the process, particularly step 1), at relatively low temperatures (e.g., 90°C or less, alternatively 80°C or less, alternatively 70°C or less, and alternatively 50°C or less) can provide improved reaction rate, yield, or both.

[0077] How to use

[0078] The above compositions and methods can be used to prepare siloxanes, intermediates and / or branched siloxane networks. Alternatively, the above compositions and methods can be used to prepare polyorganosiloxane-polyolefin hybrid copolymers, for example, when starting materials B2) and B3) are used in combination. The compositions and methods can be used to prepare formulations such as elastomers, silicone foams and paper coatings.

[0079] Example

[0080] These examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention described in the claims.The starting materials described in Table 1 and the Reference Examples were used in the Examples herein.

[0081] Table 1 - Starting materials

[0082]

[0083]

[0084] Reference Example 1 - General Procedure

[0085] Unless otherwise stated, all experimental procedures and manipulations of chemicals were performed in a nitrogen-purged glove box or Schlenk line. All bulk reaction solvents (toluene, diethyl ether, hexane, tetrahydrofuran (THF)) were dried over alumina and Q5 reactive scavenger columns. All other solvents were purchased from Aldrich anhydrous grade and activated with Molecular sieves were stored. NMR solvents (CDCl3, CD2Cl2, and C6D6) were obtained from Cambridge Isotope Laboratories, Inc. Molecular sieve drying or, in the case of C6D6, Na / K alloy drying.1-Bromo-3,5-bis(trifluoromethyl)benzene, 1-Bromo-2,5-bis(trifluoromethyl)benzene, 1-Bromo-2,6-difluorobenzene, 1-Bromo-2,4,6-trifluorobenzene and 1-Bromo-4-trifluoromethylbenzene were purchased from Oakwood Chemical.1-Bromo-2,3,5,6-tetrafluoro-4-trifluoromethylbenzene was purchased from Alfa Aesar.FAB was purchased from TCI.All other reagents were purchased from Sigma-Aldrich and used as is.Before use, n-Butyl lithium (hexane solution) was titrated using 1.00M decanol in toluene solution with 1,10-phenanthroline as indicator. 1

[0086] Multinuclear NMR spectra were collected on one of the following instruments: 1 H. 13 C. 19 F. 29 4. 11 B): Varian MR-400 or Varian VNMRS-500. 11 B NMR spectra were collected only on a Varian VNMRS-500. 1 H and 13 C NMR chemical shifts are expressed in parts per million relative to the residual solvent peak: 1 H- is 5.32 ppm for CD2Cl2, 7.15 ppm for C6D6, and 7.25 ppm for CDCl3; 13 C- is 54.00 ppm for CD2Cl2, 128.00 ppm for C6D6, and 77.00 ppm for CDCl3. 11BNMR chemical shifts were externally referenced to BF3(Et2O) (0 ppm), 19 F NMR chemical shifts were externally referenced to CFCl3 (0 ppm). Except when using dry ice or ice as the only means of cooling, subambient reaction temperatures were measured using an Extech Instruments EasyView with fine JKEM sensor PTFE wire K36INJ. TM 10Dual K model EA 10 thermometer for measurements.

[0087] Reference Example 2 - Synthesis Procedure - Preparation of Starting Materials

[0088] The preparation of lithium (diethyl etherate) (3,5-bis(trifluoromethyl)phenyl)triisopropoxyborate was carried out as follows:

[0089]

[0090] To a cold (-78°C, CO2(s) bath) solution of 1-bromo-3,5-bis(trifluoromethyl)benzene (18.52 g, 63.19 mmol) in diethyl ether (200 mL) was added n-butyl lithium (23.0 mL, 2.61 M in hexane, 60.03 mmol) with stirring. The reaction mixture was stirred at -78°C for 3 hours to form a precipitate. Triisopropyl borate (11.86 g, 63.06 mmol) in diethyl ether (20 mL) was slowly added. The reaction mixture was stirred at -78°C for 1 hour, then allowed to warm to ambient temperature and stirred for 1 hour to give a slightly turbid solution. The reaction mixture was filtered and the volatiles were removed under reduced pressure to give a solid. The solid was ground with hexane, filtered, and the volatiles were removed under reduced pressure to give the product as a colorless powder. Yield: 23.16 g, 94.53%. The compound was initially isolated as its ether adduct.

[0091] 1 H NMR (500MHz, THF-d8) δ 8.15 (s, 2H), 7.57 (s, 1H), 3.79 (p, J=6.1Hz, 3H), 0.95 (d, J=6.1Hz, 18H). 13 C NMR (126MHz, THF-d8) δ159.12, 134.71, 128.90 (q, J=31.3Hz), 125.91 (q, J=271.8Hz), 118.70, 6 7.41 (dtd, J=44.2, 22.2, 2.9Hz), 61.67, 26.53 (d, J=17.7Hz), 25.28 (dtd, J=40.4, 20.1, 3.0Hz). 19F NMR (470MHz, THF-d8) δ-63.02. 11 B NMR (160MHz, THF-d8) δ3.84.

[0092] The preparation of (3,5-bis(trifluoromethyl)phenyl)diisopropoxyborane was carried out as follows:

[0093]

[0094] To a solution of lithium (diethyl etherate)(3,5-bis(trifluoromethyl)phenyl)triisopropoxyborate (8.00 g, 19.6 mmol) in diethyl ether (100 mL) was added hydrogen chloride solution (12.3 mL, 2M in diethyl ether, 24.6 mmol) and a precipitate formed immediately. The reaction mixture was stirred for two hours, filtered, and the volatiles were removed under reduced pressure. The resulting residue was extracted with hexanes, filtered, and the volatiles were removed under reduced pressure to give the product as an oil. Yield: 5.10 g, 76.1%.

[0095] 1 H NMR (500 MHz, chloroform-d) δ 8.01 (d, J = 1.9 Hz, 2H), 7.89 (dt, J = 2.0, 1.0 Hz, 1H), 4.59 (hept, J = 6.1 Hz, 1H), 1.27 (d, J = 6.2 Hz, 6H). 13 C NMR (126 MHz, chloroform-d) δ 134.19, 132.85 (td, J = 3.7, 1.9 Hz), 130.85 (q, J = 32.9 Hz), 123.67 (d, J = 272.6 Hz), 123.04 (hept, J = 3.9 Hz), 67.00, 24.58. 19 F NMR (470 MHz, chloroform-d) δ -63.34. 11 B NMR (160 MHz, chloroform-d) δ 26.66.

[0096] The preparation of lithium (diethyl etherate) bis(3,5-bis(trifluoromethyl)phenyl)diisopropoxyborane was carried out as follows:

[0097]

[0098] To a cold (-78°C, CO2(s) bath) solution of 1-bromo-3,5-bis(trifluoromethyl)benzene (4.26 g, 14.5 mmol) in diethyl ether (200 mL) was added n-butyl lithium (5.30 mL, 2.61 M in hexane, 60.0 mmol) with stirring. The reaction mixture was stirred at -78°C for 1 hour to form a precipitate. (3,5-bis(trifluoromethyl)phenyl)diisopropoxyborane (4.82 g, 14.1 mmol) in diethyl ether (15 mL) was slowly added. The reaction mixture was stirred at -78°C for 1 hour (some solids were visible), then allowed to warm to ambient temperature and stirred overnight to give a clear solution. Volatiles were removed under reduced pressure to give a crystalline solid. The solid was dissolved in hexane, and the solution was filtered and placed in a freezer over the weekend. A large amount of crystalline material was formed. The supernatant was decanted, and the volatiles were removed under reduced pressure to give a colorless crystalline material. Material yield: 8.23 ​​g, 93.5%.

[0099] 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.99 (d, J = 1.9 Hz, 2H), 7.74 (dt, J = 1.8, 1.0 Hz, 1H), 3.81 (q, J = 7.1 Hz, 2H), 3.35 (hept, J = 6.1 Hz, 1H), 1.45 (t, J = 7.1 Hz, 3H), 0.78 (d, J = 6.1 Hz, 6H). 13 C NMR (101 MHz, chloroform-d) δ 153.43, 134.19-133.42 (m), 129.51 (q, J=31.9 Hz), 124.42 (q, J=272.4 Hz), 119.68 (hept, J=4.0 Hz), 66.83, 63.03, 25.48, 14.66. 19 F NMR (376 MHz, chloroform-d) δ -63.05. 11 B NMR (160 MHz, chloroform-d) δ 5.12.

[0100] The preparation of bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane was carried out as follows:

[0101]

[0102] To a solution of lithium (diethyl etherate)bis(3,5-bis(trifluoromethyl)phenyl)diisopropoxyborate (5.00 g, 7.86 mmol) in diethyl ether (100 mL) was added hydrogen chloride solution (5.5 mL, 2M in diethyl ether, 11 mmol) and a precipitate formed immediately. The reaction mixture was stirred for one hour and the volatiles were removed under reduced pressure. The residue was extracted with hexanes, filtered, and the volatiles were removed under reduced pressure to give the product as a colorless powder. Yield: 3.98 g, 102% (some residual solvent was present).

[0103] 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.00 (ddd, J = 2.2, 1.4, 0.7 Hz, 2H), 7.98 (dq, J = 1.9, 0.6 Hz, 4H), 4.54 (hept, J = 6.1 Hz, 1H), 1.37 (d, J = 6.1 Hz, 6H). 13 C NMR (101 MHz, chloroform-d) δ 138.42, 133.32, 131.36 (q, J = 33.2 Hz), 124.39 (p, J = 3.8 Hz), 123.39 (d, J = 272.8 Hz), 71.74, 24.62. 19 F NMR (376 MHz, chloroform-d) δ -63.33. 11 B NMR (160 MHz, chloroform-d) δ 41.80.

[0104] Synthesis procedure - preparation of catalyst

[0105] Catalyst Sample C1, tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct, was prepared as follows:

[0106] Preparation of lithium isopropoxy tris(3,5-bis(trifluoromethyl)phenyl)borate

[0107]

[0108] n-Butyl lithium (5.00 mL, 2.5 M in hexane, 12.7 mmol) was slowly added dropwise to a cold (-78°C, CO2(s) bath) solution of 1-bromo-3,5-bis(trifluoromethyl)benzene (3.76 g, 12.8 mmol) in diethyl ether (150 mL). The reaction mixture was stirred at -78°C for 1 hour. Isopropoxy-bis(3,5-bis(trifluoromethyl)phenyl)borane (6.29 g, 12.7 mmol) in ether (10 mL) was slowly added. The reaction mixture was stirred overnight while warming to ambient temperature to give a clear, very pale yellow solution. The volatiles were removed under reduced pressure to give a crystalline solid. The solid was dissolved in minimal boiling ether and the solution was placed in a freezer. After cooling overnight, the supernatant was decanted from the crystals that had formed, and the crystals were dried under reduced pressure to give 6.74 g. The supernatant solution was concentrated and cooled in the freezer overnight to give a second crop of crystalline material (1.54 g).Total yield: 8.28 g, 75.6%.

[0109] 1 H NMR (400 MHz, benzene-d6) δ 8.09 (s, 6H), 7.74 (s, 3H), 3.71 (p, J = 6.1 Hz, 1H), 2.97 (q, J = 7.0 Hz, 10H), 0.70 (t, J = 7.1 Hz, 15H), 0.67 (d, J = 6.2 Hz, 6H). 13 C NMR (101 MHz, benzene-d6) δ 157.09, 133.79, 130.75 (q, J = 32.0 Hz), 124.71 (q, J = 272.8 Hz), 119.91 (p, J = 4.2 Hz), 65.91, 65.00, 25.47, 14.11. 19 F NMR (376 MHz, benzene-d6) δ -62.76. 11 B NMR (160 MHz, benzene-d6) δ 1.56.

[0110] Preparation of tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct

[0111]

[0112] To a solution of lithium isopropoxytris(3,5-bis(trifluoromethyl)phenyl)borate (6.700 g, 7.75 mmol) in diethyl ether (100 mL) was added trimethylsilyl chloride (2.0 mL, 1.71 g, 15.8 mmol). The reaction mixture was stirred over the weekend. The reaction mixture was filtered and the volatiles were removed under reduced pressure to give the product as a colorless solid, 4.80 g, 95.2%.

[0113] A portion of the solid (4.041 g) was dissolved in ether (100 mL) and THF (5 mL) was added. The volatiles were removed from the reaction mixture under reduced pressure. The residue was extracted with benzene, filtered, and the volatiles were removed from the reaction mixture under reduced pressure to give the THF-adduct product as a colorless solid, 4.10 g, 91.3%.

[0114] THF adduct: 1 H NMR (400MHz, benzene-d6) δ7.80-7.78 (m, 6H), 7.72 (dq, J=1.8, 0.9Hz, 3H), 2.90-2.83 (m, 4H), 0.57-0.49 (m, 4H). 13 C NMR (101 MHz, benzene-d6) δ 148.11, 133.40, 131.38 (q, J = 32.5 Hz), 124.21 (q, J = 272.8 Hz), 121.37 (p, J = 4.1 Hz), 74.14, 23.94 (d, J = 2.7 Hz). 19 F NMR (376 MHz, benzene-d6) δ -62.95. 11 B NMR (160 MHz, benzene-d6) δ 11.84.

[0115] Catalyst Sample C2, bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct, was prepared as follows.

[0116] Preparation of Bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane

[0117]

[0118] N-Butyl lithium (4.70 mL, 2.535 M in hexane, 11.9 mmol) is slowly added dropwise to a cold (-78 ° C, CO2 (s) / acetone bath) solution of 1-bromo-4-trifluorotoluene (2.750 g, 12.22 mmol) in diethyl ether (200 mL). The reaction mixture is stirred at -78 ° C for 3 hours. Isopropoxybis (3,5-bis (trifluoromethyl) phenyl) borane (5.910 g, 11.91 mmol) in diethyl ether (15 mL) is slowly added. The reaction mixture is warmed to ambient temperature while stirring overnight to obtain a clear yellow solution with trace precipitation. The solvent is removed under reduced pressure to obtain a viscous yellow oil. The oil is rapidly stirred overnight with hexane (100 mL) (producing some turbidity). The hexane layer is decanted, filtered, and volatiles are removed under reduced pressure. The oil layer is extracted with hexane again and the process is repeated several times. A small amount of undissolved oily matter is discarded. Volatiles are removed from the filtrate under reduced pressure to obtain a yellow oily matter. The oily matter is dissolved in diethyl ether (100mL), and trimethylchlorosilane (1.5g, 13.8mmol) is added. A large amount of precipitation is formed in 30 minutes. The reaction mixture is stirred overnight. The reaction mixture is filtered, and volatiles are removed under reduced pressure to obtain a pasty beige sludge. The NMR spectrum shows almost complete reaction. The product is dissolved in ether and more TMSCl (0.4mL) is added. After stirring for several hours, volatiles are removed under reduced pressure. Residue is extracted with benzene, filtered, and volatiles are removed under reduced pressure to obtain a pasty solid. 1 The H NMR spectrum still shows some isopropyl groups and some ether. The residue was dissolved in ether, a small amount of TMSCl (0.2 mL) was added, and the reaction mixture was stirred for several hours. A few milliliters of THF were added, and the volatiles were removed under reduced pressure. The product was extracted with benzene, filtered, and the volatiles were removed under reduced pressure to obtain the product as a white solid (5.370 g, 68.90%).

[0119] NMR spectrum of borane-THF complex: 1 H NMR (400MHz, benzene-d6) δ7.83 (s, 4H), 7.78 (tq, J=1.7, 0.8Hz, 2H), 7.41 (dq, J=7.4, 0.8Hz, 2H), 7.07 (dq, J=7.5, 0.9Hz, 2H), 3.04-2.96 (m, 4H), 0.70-0.62 (m, 4H). 13C NMR (126MHz, benzene-d6) δ149.08, 148.88, 134.18, 133.62 (d, J=3.8Hz), 131.11 (q, J=32.4Hz), 129.94 (q, J=32.1Hz) , 125.06 (d, J=272.1Hz), 124.92 (q, J=3.8Hz), 124.34 (q, J=272.7Hz), 121.22 (dt, J=8.0, 4.0Hz), 73.53, 24.10. 19 F NMR (376 MHz, benzene-d6) δ -62.56 (s, 3F), -62.78 (s, 12F). 11 B NMR (160 MHz, benzene-d6) δ 18.54.

[0120] Catalyst Sample C3, bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct, was prepared as follows:

[0121] Preparation of Lithium Bis(Diethyl Ether)Bis(3,5-Bis(Trifluoromethyl)phenyl)(2,4,6-Trifluorophenyl)-Isopropoxyborate

[0122]

[0123] In the glove box purged by N2, 2.06g (9.78mmol) 1-bromo-2,4,6-trifluorobenzene is combined with 80mL diethyl ether in a 250mL Xileike flask. The stirring rod coated with polytetrafluoroethylene is added to the colorless solution, and the flask is sealed with a rubber septum before being taken out from the glove box. In a fume hood, the flask is connected to a nitrogen line, and is placed in a dry ice / acetone bath (-78°C) and frozen for 20 minutes. A solution of 2.5M n-butyl lithium in hexane (4.3mL, 10.8mmol) is added to the cold solution via a syringe. The reaction mixture is stirred at -78°C for 1 hour. A solution of 4.85g bis (3,5-bis (trifluoromethyl) phenyl) isopropoxy borane in 20mL diethyl ether is prepared in a glove box, and drawn into a syringe. The solution is injected into the flask containing a cold aryl lithium solution at -78°C, and the mixture is stirred at this temperature for half an hour. Remove the dry ice / acetone bath, and allow the reaction mixture to slowly warm to room temperature while stirring overnight. The next morning, all volatiles were removed under vacuum to obtain a sticky yellow solid. The flask was returned to the glove box, and the sticky yellow material was extracted with 1) 80 mL pentane, 2) 80 mL hexane and 3) 60 mL 50 / 50 ether / hexane mixture. All three solutions were placed in a glove box freezer overnight (-40 ° C) and white crystalline material was precipitated from the solution. The crystalline material was collected by filtration, washed with cold pentane (-40 ° C), and dried under vacuum for 1 hour. Total yield: 5.29 g (impure, about 5.5 mmol desired lithium salt, 56%). It should be noted that no pure material was obtained; the lithium salt was contaminated by isopropoxyborane starting material (12%-22% contaminated, depending on the solid material batch collected). It was decided to proceed to the next step in the reaction without any further purification of the separated material.

[0124] 1 H NMR (400 MHz, benzene-d6) δ 8.26 (s, 4H, o-ArCH), 7.80 (s, 2H, p-ArCH), 6.22-6.07 (m, 2H, o-ArCH), 3.68 (hept, J = 5.8 Hz, 1H, CH(CH3)2), 3.07 (q, J = 7.1 Hz, 8H, OCH2), 0.81 (t, J = 7.1 Hz, 12H, OCH2CH3), 0.67 (d, J = 6.2 Hz, 6H, CH(CH3)2). 13C NMR (101 MHz, benzene-d6) δ 166.2 (ddd, J = 231.3, 22.4, 14.0 Hz, ArC), 162.3 (dt, J = 247.1, 20.2 Hz, ArC), 159.5 (br s, ArC), 157.3 (br s, ArC), 133.8 (s, o-ArCH), 130.7 (q, J = 31.9 Hz, ArC-CF3), 125.5 (q, J = 272.4 Hz, CF3), 119.9 (p, J = 4.0 Hz, p-ArCH), 101.0 (ddd, J = 36.6, 24.0, 3.7 Hz, m-ArCH), 65.9 (s, OCH(CH3)2), 65.8 (s, OCH2CH3), 25.7 (s, OCH(CH3)2), 14.7 (s, OCH2CH3). 19 F NMR (376 MHz, benzene-d6) δ -62.7 (s, 12F, CF3), -104.4 (br s, 2F, o-ArF), -112.3 (m, 1F, p-ArF).

[0125] Preparation of Bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoro)borane

[0126]

[0127] In a N2 purged glove box, 3.30 g (78% purity, 3.29 mmol) of lithium borate salt was dissolved in 60 mL of diethyl ether to form a colorless solution (Note: borane lithium salt was contaminated with 22% bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane). Trimethylsilyl chloride (1.0 mL, 7.9 mmol) was added to the solution under stirring at room temperature. There was no sign of immediate reaction. The mixture was stirred at room temperature overnight. The next morning, a large amount of LiCl precipitate formed in the flask. An aliquot of the reaction mixture was taken out and the mixture was filtered off by evaporation. 19 F NMR spectroscopy was performed to confirm that the reaction was complete. The reaction mixture was filtered through diatomaceous earth to remove LiCl, and the filtrate was evacuated to dryness. The resulting sticky white solid was extracted with 80-90mL hexane and filtered again. The hexane solution was placed in a glove box freezer overnight (-40°C), during which time a white microcrystalline solid was precipitated. The solid was collected by filtration, washed with 5-10mL cold pentane (-40°C), and dried under vacuum for 1 hour. Multinuclear NMR spectroscopy confirmed that the desired substance in pure form was formed. Yield: 0.992g, 1.75mmol, 53.2%.

[0128] 1H NMR (400 MHz, benzene-d6) δ 7.88 (s, 6H, ArCH on the CF3-substituted ring), 6.03 (m, 2H, ArCH on the 2,4,6-trifluorobenzene ring). 13 C NMR (101 MHz, benzene-d6) δ 167.4 (dt, J = 257.6, 16.2 Hz, p-ArCF), 166.2 (dt, J = 253.5, 15.2 Hz, o-ArCF), 142.8 (br s, ArC), 137.5 (d, J = 3.0 Hz, o-ArCH), 132.1 (q, J = 33.4 Hz, ArC-CF3), 126.9 (pent, J = 4.0 Hz, p-ArCH), 124.1 (q, J = 273.0 Hz, CF3), 112.6 (br s, ArC), 101.6 (ddd, J = 29.0, 24.9, 3.7 Hz, m-ArCH). 19 F NMR (376 MHz, benzene-d6) δ -63.1 (s, 12F, CF3), -92.4 (m, 2F, o-ArCF), -98.5 (s, 1F, p-ArCF). 11 B NMR (160 MHz, benzene-d6) δ 62.9 (broad s).

[0129] Preparation of THF adduct of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoro)borane

[0130]

[0131] In a N2 purged glove box, 0.992 g (1.75 mmol) bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane was weighed into a 110 mL glass jar and dissolved in 50 mL THF. The THF was removed under vacuum with stirring to produce a white solid. The solid was triturated with 40 mL pentane to help remove any uncoordinated THF. The white solid was characterized by multinuclear NMR spectroscopy as the mono-THF adduct of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoro-phenyl)borane. Yield: 0.969 g, 1.51 mmol, 86.3%.

[0132] 1 H NMR (400 MHz, benzene-d6) δ 7.96 (s, 4H, o-ArCH), 7.79 (s, 2H, p-ArCH), 6.16 (t, J=8.0 Hz, 2H, m-ArCH), 3.10 (m, 4H, OCH2), 0.79 (m, 4H, CH2). 13C NMR (101 MHz, benzene-d6) δ 165.3 (ddd, J = 245.4, 17.7, 14.3 Hz, o-ArCF), 163.9 (dd, J = 249.5, 16.2 Hz, p-ArCF), 148.4 (brs, ArC), 134.0 (s, o-ArCH), 131.4 (q, J = 32.4 Hz, ArC-CF3), 121.8 (m, p-ArCH), 124.8 (q, J = 272.7 Hz, CF3), 101.3 (ddd, J = 32.8, 24.2, 3.2 Hz, m-ArCH), 72.6 (s, OCH2), 24.8 (s, CH2). 19 FNMR (376 MHz, benzene-d6) δ -62.8 (s, 12F, CF3), -96.9 (s, 2F, o-ArCF), -108.5 (s, 1F, p-ArCF). 11 B NMR (160 MHz, benzene-d6) δ 13.2 (broad s).

[0133] Catalyst Sample C4, bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)THF adduct, was prepared as follows:

[0134] Preparation of Lithium Bis(Diethyl Ether)Bis(3,5-Bis(Trifluoromethyl)phenyl)(2,6-Difluorophenyl)-Isopropoxyborate

[0135]

[0136] n-Butyl lithium (3.00 mL, 2.48 M in hexane, 7.44 mmol) was slowly added dropwise to a cold (-78 ° C, CO2 (s) bath) solution of 1-bromo-2,6-difluorobenzene (1.46 g, 7.56 mmol) in diethyl ether (100 mL). The reaction mixture was stirred at -78 ° C for 1 hour, and then a solution of bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane (3.69 g, 7.44 mmol) in diethyl ether (10 mL) was slowly added. A precipitate was formed while the reaction mixture was warmed to ambient temperature. By the time the reaction mixture had reached room temperature, the precipitate dissolved to give a clear solution, which was stirred for several hours. The solution was filtered and volatiles were removed under reduced pressure to give a crystalline solid. The solid was dissolved in minimal boiling ether, and the solution was placed in a glove box freezer (-33 ° C). After cooling overnight, the supernatant was decanted from the crystals that had formed. The crystals were dried under reduced pressure. Yield: 6.85 g, 88.4%.

[0137] 1H NMR (400MHz, benzene-d6) δ8.31 (s, 4H), 7.77 (tt, J=2.0, 0.9Hz, 2H), 6.60 (dq, J=8.8, 7.5Hz, 1H), 6.47-6.41 (m, 2H) , 3.71 (hept, J=6.2Hz, 1H), 3.05 (qd, J=7.1, 0.7Hz, 8H), 0.82 (td, J=7.1, 0.6Hz, 12H), 0.68 (d, J=6.2Hz, 6H). 13 C NMR (126MHz, benzene-d6) δ164.45 (dd, J=249.6, 11.3Hz), 142.11, 137.21, 136.78 (t, J=3.8Hz), 135.51 (t, J=10.8Hz), 1 31.28 (q, J=33.3Hz), 126.10 (p, J=3.8Hz), 123.30 (q, J=273.1Hz), 111.72-111.40 (m), 73.82, 65.57, 15.11, 2.57. 19 F NMR (376 MHz, benzene-d6) δ -62.64, -106.66. 11 B NMR (160 MHz, benzene-d6) δ 0.68 (s).

[0138] Preparation of THF adduct of bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane

[0139]

[0140] Lithium bis(diethyl etherate)bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)isopropoxyborate (5.85 g, 10.6 mmol) was dissolved in diethyl ether (150 mL) and trimethylsilyl chloride (3.00 mL, 23.6 mmol) was added to the solution at ambient temperature. A precipitate began to form within 15 minutes. The reaction mixture was allowed to stir over the weekend. By Monday, the volatiles had evaporated (non-sealed container). The colorless solid was extracted with diethyl ether and filtered. The volatiles were removed under reduced pressure to give the product as a colorless solid, 4.98 g. The NMR spectrum showed pure borane, but only about 86% of the desired diethyl ether for the monoetherate complex. The product was dissolved in diethyl ether to give a turbid solution. THF (6 mL) was added and the solution became crystalline and transparent. The volatiles were removed under reduced pressure to give a glassy solid. The residue was extracted with benzene, filtered, and the volatiles were removed under reduced pressure to give a white solid. Yield: 4.63 g, 69.9%.

[0141] 1H NMR (400MHz, benzene-d6) δ8.02 (d, J=1.8Hz, 2H), 7.77 (dq, J=1.9, 0.9Hz, 1H), 6.7 1-6.60 (m, 0H), 6.48 (t, J=8.4Hz, 1H), 3.17-3.09 (m, 2H), 0.77-0.68 (m, 2H). 13C NMR (101 MHz, benzene-d6) δ 164.82 (dd, J = 243.3, 14.1 Hz), 147.95, 133.82, 133.30, 130.91 (d, J = 32.4 Hz), 124.41 (q, J = 272.8 Hz), 121.40 (q, J = 3.9 Hz), 112.57-111.60 (m), 73.58, 24.03 (d, J = 3.3 Hz). 19 F NMR (376 MHz, benzene-d6) δ -62.80, -99.69 (t, J = 7.5 Hz). 11 B NMR (160 MHz, benzene-d6) δ 12.2 (s).

[0142] Catalyst Sample C5, bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane, was prepared as follows:

[0143] Preparation of lithium isopropoxybis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate

[0144]

[0145] n-Butyl lithium (4.00 mL, 2.535 M in hexane, 10.14 mmol) was slowly added to a cold (-78 ° C, CO2 (s) bath) solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (3.00 g, 10.24 mmol) in diethyl ether (200 mL). The reaction mixture was stirred at -78 ° C for 1 hour. Isopropoxy-bis(3,5-bis(trifluoromethyl)phenyl)borane (5.036 g, 10.15 mmol) in diethyl ether (18 mL) was slowly added. The reaction mixture was stirred at -78 ° C for several hours. The solution was warmed to ambient temperature while stirring overnight to obtain a light yellow clear solution. Volatiles were removed from the reaction mixture to obtain a yellow oil. The oil was extracted with benzene. There was no insoluble matter. Volatiles were removed from the reaction mixture to obtain a yellow oil. The yield was 7.88 g, 98.3%.

[0146] 1H NMR (400MHz, benzene-d6) δ8.06 (s, 1H), 8.00 (s, 4H), 7.70 (dt, J=1.8, 0.9Hz, 2H), 7.40 (d, J=8.3Hz, 1H), 7.19 (d, J =8.4Hz, 1H), 3.79 (hept, J=6.1Hz, 1H), 2.78 (q, J=7.1Hz, 4H), 0.73 (d, J=6.1Hz, 6H), 0.54 (t, J=7.1Hz, 6H). 13 C NMR (101MHz, benzene-d6) δ158.31, 153.97, 135.44 (q, J=3.7Hz), 135.23, 133.5 5(t, J=4.1Hz), 133.25, 133.18, 132.37 (d, J=97.8Hz), 130.92 (q, J=32.0H z), 127.80 (q, J=273.9Hz), 124.92 (q, J=272.5Hz), 124.66 (q, J=272.8Hz ), 123.86 (q, J=3.8Hz), 119.86 (p, J=3.9Hz), 66.24, 66.17, 25.60, 13.94. 19 F NMR (376 MHz, benzene-d6) δ -55.30--55.51 (m), -62.82, -63.61. 11 B NMR (160 MHz, benzene-d6) δ 2.16.

[0147] Preparation of Bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane

[0148]

[0149] Lithium (diethyl ether) isopropoxy-bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate (7.88 g, 9.97 mmol) was dissolved in diethyl ether (150 mL). Trimethylchlorosilane (2.6 mL, 20.5 mmol) was added. The reaction mixture was stirred overnight to give a yellow solution with a colorless precipitate. All volatiles were removed under reduced pressure. The residue was extracted with hexane (100 ml). The mixture was filtered and the volatiles were concentrated under reduced pressure. The solution was cooled in a freezer (-33 ° C) overnight. The reaction mixture was filtered and the precipitate was dried under reduced pressure to give a white powder. Yield: 6.0182 g, 92.84%.

[0150] Compounds without THF: 1H NMR (400 MHz, benzene-d6) δ 7.87 (s, 2H), 7.85 (s, 4H), 7.29 (s, 1H), 7.11 (d, J=1.2 Hz, 2H). 13 C NMR (126MHz, benzene-d6) δ140.87, 140.75, 137.49 (d, J=3.8Hz), 135.11 (q, J=31.7Hz), 133.26 (q, J=33.0Hz), 132.03 (q, J=33.6Hz), 128.29, 127.34 (q, J=3.8Hz), 127.11 (q, J=4.0Hz), 127.01 (q, J=4.0Hz), 124.46 (q, J=274.3Hz), 123.70 (q, J=273.2Hz), 123.49 (q, J=272.9Hz). 19 F NMR (376 MHz, benzene-d6) δ -56.98, -63.43, -63.47. 11 BNMR (160 MHz, benzene-d6) δ 64.37.

[0151] Catalyst sample C6, (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane, was prepared as follows:

[0152] Preparation of lithium diisopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate

[0153]

[0154] To a cold (between -101°C and -99°C, CO2(s), then N2(1) methanol bath) solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (3.000 g, 10.24 mmol) in diethyl ether (150 mL) was added n-butyl lithium (4.00 mL, 2.535 M in hexane, 10.14 mmol) with stirring. The reaction mixture was stirred at about -100°C for 2 hours and then allowed to warm to -78°C. Bis(isopropoxy)(3,5-bis(trifluoromethyl)phenyl)borane (3.510 g, 10.26 mmol) in diethyl ether (10 mL) was slowly added. The reaction mixture was allowed to warm to ambient temperature while stirring overnight. Volatiles were removed from the pale yellow, almost clear solution under reduced pressure to give a crystalline solid. The solid was dissolved in diethyl ether (10 mL) and placed in a freezer. No precipitation. The ether was evaporated and the yellow solid was dissolved in hexane, filtered and concentrated under a stream of nitrogen to give a crystalline solid. The supernatant was removed and the solid was dried under reduced pressure. Yield of colorless crystals from the first batch: 3.318 g. NMR analysis of the crystals showed pure desired compound. The supernatant was placed in a freezer overnight. A crystalline material was formed. The supernatant was sucked off and discarded. The crystalline residue was dried under reduced pressure: 2.017 g. Total yield: 5.335 g, 82.79%.

[0155] 1 H NMR (400MHz, benzene-d6) δ8.39 (s, 2H), 8.26 (s, 1H), 7.90 (dq, J=1.8, 0.9Hz, 1H), 7.56 (d, J=8.2Hz, 1H), 7.27 (ddt, J=7.9, 1.7, 0.8 Hz, 1H), 3.18 (hept, J=6.0Hz, 2H), 2.92 (q, J=7.1Hz, 4H), 0.89 (t, J=7.1Hz, 6H), 0.78 (d, J=6.1Hz, 6H), 0.68 (d, J=6.0Hz, 6H). 13 C NMR (101MHz, benzene-d6) δ153.10, 136.65 (q, J=29.6Hz), 134.81 (dd, J=2.7Hz, 1.9 Hz), 133.93 (q, J=3.6Hz), 131.93 (q, J=31.6Hz), 131.35, 129.76 (q, J=31.9H z), 127.26 (q, J=274.6Hz), 125.17 (d, J=272.4Hz), 124.89 (q, J=272.8Hz), 1 23.25 (q, J=3.9Hz), 119.89 (p, J=3.9Hz), 66.42, 64.08, 25.49, 24.57, 14.36. 19F NMR (376 MHz, benzene-d6) δ -55.79, -62.66, -63.30. 11 B NMR (160 MHz, benzene-d6) δ 5.32.

[0156] Preparation of isopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane

[0157]

[0158] To a solution of lithium (diethyl ether)diisopropoxy-(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate (3.318 g, 5.21 mmol) in diethyl ether (10 mL) was added trimethylchlorosilane (2.0 mL) and a precipitate quickly formed. The reaction mixture was allowed to stir overnight. The reaction mixture was filtered and the volatiles were removed under reduced pressure. NMR analysis showed that the reaction was complete. Some putative TMS-O-iPr ether was also present. A second batch of lithium diisopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate (2.017 g, 3.17 mmol, lithium salt; 2.0 mL TMSCl) prepared as described above was treated similarly and stirred for 3 hours. Total amount of combined reagents: 5.335 g, 8.39 mmol; TMSCl: 4.0 mL, 31.6 mmol. The second reaction mixture was filtered and combined with the first reaction product. All volatiles were removed under reduced pressure. The residue was extracted with hexanes, filtered, and the volatiles were removed under reduced pressure at 40°C overnight to give the product as a yellow oil, 3.4703 g, 83.42%.

[0159] 1 H NMR (400MHz, benzene-d6) δ8.05 (d, J=1.8Hz, 2H), 7.80 (d, J=2.3Hz, 1H), 7.34 (d, J=1.9Hz, 1H), 7. 12 (d, J=6.5Hz, 1H), 7.10 (d, J=6.7Hz, 1H), 3.78 (hept, J=6.1Hz, 1H), 0.85 (d, J=6.1Hz, 6H). 13C NMR (101MHz, benzene-d6) δ139.07, 136.28, 135.37 (q, J=31.8Hz), 134.93 (d, J=3.9Hz), 133.49 (q, J=32.7Hz), 131.50 (q, J=33.0Hz), 127.87, 126.95 (dq, J=7.5, 3.7Hz), 126.46 (q, J=3.7Hz), 125.41 (hex, J=3.8Hz), 124.57 (q, J=273.9Hz), 123.98 (q, J=272.8Hz), 123.90 (q, J=273.0Hz), 72.49, 23.71. 19 F NMR (376 MHz, benzene-d6) δ -60.31, -63.27 (d, J = 3.3 Hz), -63.47 (d, J = 3.3 Hz). 11 B NMR (160 MHz, benzene-d6) δ 41.28.

[0160] Preparation of lithium isopropoxybis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borate

[0161]

[0162] n-Butyl lithium (2.40 mL, 2.535 M in hexane, 6.08 mmol) was slowly added to a cold (-78 ° C, CO2 (s) bath) solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (1.800 g, 6.14 mmol) in diethyl ether (150 mL). The reaction mixture was stirred at -78 ° C for 1 hour. Isopropoxy(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borane (3.022 g, 6.09 mmol) in diethyl ether (18 mL) was slowly added. The reaction mixture was stirred at -78 ° C for several hours. The solution was allowed to warm to ambient temperature while stirring overnight to give a pale yellow clear solution. Volatiles were removed from the reaction mixture to give a yellow oil. The oil was extracted with benzene. There was no insoluble matter. Volatiles were removed from the reaction mixture to give a yellow oil. The yield was 4.21 g, 87.6%.

[0163] 1H NMR (400MHz, benzene-d6) δ8.30 (s, 2H), 8.12 (s, 2H), 7.65 (dt, J=1.7, 0.9Hz, 1H), 7.27 (d, J=8.2Hz, 2H), 7.08 (d, J =8.2Hz, 2H), 3.87 (hept, J=6.2Hz, 1H), 2.91 (q, J=7.1Hz, 4H), 0.65 (d, J=6.2Hz, 6H), 0.63 (t, J=7.1Hz, 6H). 13 C NMR (101MHz, benzene-d6) δ157.17, 156.73, 134.42, 133.88 (q, J=3.6Hz), 133.04 (d, J=28.4Hz), 132.88 (q, J=32.1Hz), 129.95 (q, J=31.9Hz), 127.74 (q, J=2 73.6Hz), 127.33 (q, J=6.9Hz), 124.97 (q, J=272.4Hz), 124.50 (q, J=273.0H z), 122.72 (q, J=3.8Hz), 118.78 (p, J=4.1Hz), 65.88, 65.34, 25.11, 13.91. 19 F NMR (376 MHz, benzene-d6) δ -56.31, -62.89, -63.76. 11 B NMR (160 MHz, benzene-d6) δ 2.98.

[0164] Preparation of Bis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borane

[0165]

[0166] To a solution of (diethyl ether)isopropoxy-bis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borate lithium (3.915 g, 4.95 mmol) in diethyl ether (150 mL) was added trimethylchlorosilane (1.10 mL, 10.1 mmol) with stirring. Within 15 minutes, a precipitate formed in the solution. The reaction mixture was stirred overnight. The mixture was filtered and the volatiles were removed under reduced pressure to give a colorless solid, 3.260 g. The product was extracted with hexane, filtered, and the volatiles were removed under reduced pressure to give the product as a light solid, 3.109 g, 96.53%.

[0167] 1 H NMR (500 MHz, benzene-d6) δ 7.90 (s, 1H), 7.83 (s, 1H), 7.66 (s, 3H), 7.09 (s, 5H), 7.09 (s, 5H).13 C NMR (126MHz, benzene-d6) δ141.54, 140.05, 138.35 (q, J=3.8Hz), 135.84 (q, J=32.0Hz), 133.02 (q, J=33.0Hz), 132.02 (q, J=33.7Hz), 129.98 ( q, J=3.5Hz), 128.29, 127.91 (d, J=2.4Hz), 127.13 (q, J=4.2Hz), 124.15 (q, J=274.2Hz), 123.70 (q, J=273.2Hz), 123.37 (q, J=273.2Hz). 19 F NMR (470 MHz, benzene-d6) δ -56.40, -63.31, -63.58. 11 BNMR (160 MHz, benzene-d6) δ 67.58.

[0168] Catalyst sample C7 was prepared as follows:

[0169] Preparation of tris(2,5-bis(trifluoromethyl)phenyl)borane

[0170]

[0171] The reaction was performed in a manner similar to previously reported procedures. 2 Isopropylmagnesium chloride-lithium chloride (46.0 mL, 58.0 mmol, 1.26 M in THF) was added to a solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (17.05 g, 58.2 mmol) in THF (250 mL) in an acetone bath cooled with dry ice (-76 ° C). After the addition was complete, the reaction flask was transferred to an ice bath (0 ° C) and the reaction mixture was stirred for 2 hours. The reaction mixture was cooled to -78 ° C and 15 mL of boron trifluoride diethyl etherate (2.43 mL, 2.74 g, 19.3 mmol) in ether was added. The reaction mixture was allowed to warm to room temperature while stirring it over the weekend. Volatiles were removed from the solution to give a reddish solid, 12.77 g. The residue was extracted with toluene and filtered. Volatiles were removed under reduced pressure to give a pink powder, 10.75 g. The solid was extracted with dichloromethane to give a light purple solution. The solution was placed in a freezer overnight. The supernatant was decanted from the very light pink crystalline material that formed. The material was dried overnight under reduced pressure. Yield: 7.0003 g, 55.73%.

[0172] Products without TH: 1H NMR (400 MHz, benzene-d6) δ 7.57 (s, 1H), 7.13 (s, 3H), 7.08 (dd, J=8.3, 1.8 Hz, 3H). 13 C NMR (101MHz, benzene-d6) δ141.10, 136.50 (q, J=32.2Hz), 132.81 (q, J=33.1Hz), 131.59 (q, J=3.8Hz), 128.85 (q, J=3.7Hz), 127.45 (q, J=3.4, 2.1Hz), 123.93 (q, J=274.6Hz), 123.59 (q, J=273.1Hz). 19 F NMR (376 MHz, benzene-d6) δ -56.48, -63.77. 11 B NMR (160 MHz, benzene-d6) δ 68.81.

[0173] Catalyst sample C8, bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct, was prepared as follows:

[0174] Preparation of (tetrahydrofuran)bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)isopropoxy lithium borate

[0175]

[0176] n-Butyl lithium (3.00 mL, 2.54 M in hexane, 7.61 mmol) was added to a cold (between -101°C and -99°C, CO2(s), then N2(1) methanol bath) solution of 1-bromo-2,3,5,6-tetrafluoro-4-trifluorotoluene (2.26 g, 7.61 mmol) in diethyl ether (100 mL) under stirring. The reaction mixture was stirred at -100°C for 2 hours and then allowed to warm to -76°C. Bis(3,5-bis(trifluoromethyl)phenyl)isopropoxy-borane (3.78 g, 7.61 mmol) in diethyl ether (10 mL) was slowly added to the reaction mixture. The reaction mixture was slowly warmed to ambient temperature while stirring overnight. The next day, the pale yellow, almost clear solution was filtered, and the volatiles were removed from the filtrate under reduced pressure to give a crystalline solid. The solid was washed with hexane, filtered and dried under reduced pressure. An aliquot of the solid was taken for NMR analysis. It has limited solubility in benzene. An aliquot was dissolved in THF and the volatiles removed under reduced pressure and then analyzed again by NMR in benzene. Yield: 6.16 g, 93.2%.

[0177] 1H NMR (500MHz, benzene-d6) δ 8.32 (s, 4H), 7.85 (s, 2H), 3.47 (h, J=6.2Hz, 1H), 3.26-3.17 (m, 4H), 1.24-1.16 (m, 4H), 0.55 (d, J=6.2Hz, 6H). 13 C NMR (126MHz, benzene-d6) δ 144.07 (d, J = 259.4Hz), 134.41, 133.82, 133.48 (d, J = 187.5Hz), 130.59 (q, J = 32.2Hz), 130.45 (q, J = 31.8Hz), 126.40-1 23.43 (m), 125.84, 124.97 (q, J=272.4Hz), 119.94 (p, J=4.0Hz), 118.92 (d, J=190.9Hz), 109.57 (d, J=22.7Hz), 68.38, 65.30, 25.64, 25.13. 19 F NMR (470 MHz, benzene-d6) δ -56.26 (t, J = 20.7 Hz), -62.59, -137.04, -141.73. 11 B NMR (160 MHz, benzene-d6) δ 1.20.

[0178] Preparation of Bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane Tetrahydrofuran THF Adduct

[0179]

[0180] To a solution of lithium (tetrahydrofuranyl)bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)isopropoxyborate (6.16 g, 7.10 mmol) in diethyl ether (100 mL) was added trimethylsilyl chloride (2.00 mL, 18.4 mmol) with stirring. The reaction mixture was stirred overnight. The next day, the reaction mixture was heated to 40 ℃ and then stirred for 2 hours. The reaction mixture was stirred for 2 hours. The reaction mixture was stirred for 3 ... 19 F NMR spectroscopy analysis of an aliquot of the reaction mixture revealed no reaction. A solution of hydrogen chloride in diethyl ether (7.00 mL, 2.0 M, 14.0 mmol) was added and the reaction mixture was stirred overnight. The next day, the reaction mixture was stirred overnight by 19F NMR spectroscopy analysis of an aliquot of the reaction mixture revealed that the reaction was complete. The mixture was filtered and the volatiles were removed from the filtrate under reduced pressure. The resulting residue was dissolved in toluene, filtered, and the volatiles were removed from the filtrate under reduced pressure to give 4.50 g of crude product. The colorless pasty solid was washed with hexane and filtered to give a colorless powder which was dried under reduced pressure. NMR analysis of the powder revealed that one molecule of isopropanol was retained in the coordination sphere of borane. Yield of borane as isopropanol adduct: 2.45 g, 52.8%.

[0181] A portion of borane isopropanol adduct (1.811 g) was dissolved in ether (40 mL) and THF (10 mL) was added to the solution. The solution was slowly evaporated to obtain large crystals. The supernatant was removed and the very light yellow crystals were washed with hexane. The crystals were dried under reduced pressure (1.08 g). The crystals were analyzed by X-ray crystallography and found to be borane isopropanol adducts. THF did not replace the coordinated alcohol. The supernatant solution and hexane washings from the crystals were combined and concentrated under vacuum to obtain a second batch of crystals (0.422 g). The second batch of crystals was washed and dried in the same manner as the first batch. NMR analysis showed the presence of coordinated isopropanol, but little or no THF. THF was added and then volatiles were removed under reduced pressure. NMR analysis showed the presence of THF, but there was still some isopropanol. The solid was dissolved in THF and then pumped out. Repeat five more times to obtain a THF adduct as a white powder. Yield: 0.413 g, 22.4%.

[0182] THF adduct:

[0183] 1 H NMR (400MHz, benzene-d6) δ7.87 (s, 4H), 7.80 (s, 4H), 3.02-2.93 (m, 4H), 0.78-0.72 (m, 4H). 13 C NMR (126MHz, benzene-d6) δ147.98 (td, J=16.5, 3.6Hz), 146.05 (tt, J=11.8, 4.1Hz), 145.58 (d, J=20.9Hz), 143.50 (d, J=20.1Hz), 133.4 4, 131.39 (q, J=32.6Hz), 124.24 (q, J=272.7Hz), 121.78 (t, J=4.0Hz), 121.45 (q, J=274.4Hz), 109.38-108.10 (m), 73.75, 23.90. 19F NMR (376 MHz, benzene-d6) δ -56.57 (t, J = 21.0 Hz), -62.95, -130.60 (dd, J = 22.5, 13.2 Hz), -140.71 (qt, J = 19.7, 8.6 Hz). 11 B NMR (160 MHz, benzene-d6) δ 7.22.

[0184] A catalyst sample prepared as described above in Reference Example 2 is shown below.

[0185]

[0186] The structures of fluorinated aryl borane Lewis acid catalyst samples C1-C8 and commercially available FAB are shown above. Structure C1 is tris (3, 5-bis (trifluoromethyl) phenyl) borane THF adduct (corresponding to the starting material A1 in the claims). Structure C2 is bis (3, 5-bis (trifluoromethyl) phenyl) (4-trifluoromethyl phenyl) borane THF adduct (corresponding to the starting material A2 in the claims). Structure C3 is bis (3, 5-bis (trifluoromethyl) phenyl) (2, 4, 6-trifluorophenyl) borane THF adduct (corresponding to the starting material A3 in the claims). Structure C4 is bis (3, 5-bis (trifluoromethyl) phenyl) (2, 6-difluorophenyl) borane THF adduct (corresponding to the starting material A4 in the claims). Structure C5 is bis (3, 5-bis (trifluoromethyl) phenyl) (2, 5-bis (trifluoromethyl) phenyl) borane (corresponding to the starting material A5 in the claims). Structure C6 is (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane (corresponding to the starting material A6 in the claims). Structure C7 is tris(2,5-bis(trifluoromethyl)phenyl)borane. Structure C8 is bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct (corresponding to the starting material A7 in the claims).

[0187] Reference Example 3 - General Procedure

[0188] HTMS, PMDS, TES, TMSOMe and FAB (described above in Table 1) were used as received. In a nitrogen-purged glove box, a solution of a fluorinated triarylborane Lewis acid sample (catalyst) was prepared in a 10 mL glass vial (Example: FAB, 30.7 mg, 0.06 mmol dissolved in 5 mL of anhydrous deuterated benzene). A silicon hydride (Example: HTMS, 32.6 μL, 0.12 mmol, 1 equiv), an organosilicon compound with an alkoxy group (Example: trimethylmethoxysilane, 17 μL, 0.12 mmol, 1 equiv), and an internal standard (mesitylene, 16.8 μL, 0.12 mmol, 1 equiv) were placed in an NMR tube. The catalyst (0.5 mL, 0.006 mmol, 5 mol%) was delivered by pipette as a stock solution. The final concentration of the solution was 0.24 M. The tube was capped and the samples were taken at regular time intervals. 1 H NMR spectroscopy. Conversion was determined using 400 MHz NMR compared to an internal standard.

[0189] All fluorinated triarylborane Lewis acid samples tested, except C7, catalyzed the SiH—SiOR cure reaction under the conditions tested. Without being bound by theory, it is believed that C7 is sterically too large to catalyze the reaction under these conditions, and this also demonstrates that not all fluorinated arylboranes will catalyze the reaction.

[0190]

[0191] Reaction scheme using various silicon hydrides and fluorinated triarylboranes

[0192] Table 1: Reaction results at room temperature

[0193]

[0194] Without being bound by theory, it is believed that TES is more difficult to react than HMTS, which is more difficult to react than PMDS, and that C6 will yield higher conversions at higher temperatures.

[0195] Industrial Applicability

[0196] The compositions and methods described herein employ fluorinated triaryl borane Lewis acids as catalysts. These fluorinated triaryl borane Lewis acids provide better reaction rate control than FAB. The compositions and methods described herein provide the following additional benefits: the order of addition of the starting materials is not critical; the starting materials can be combined in any order. The compositions and methods of the present invention can provide benefits in terms of pot life and / or process robustness. Without being bound by theory, it is believed that silicon-based hydrides should not be mixed with FAB because this will trigger self-curing.

[0197] Definition and usage of terms

[0198] Abbreviations used in the specification have the definitions in Table 5 below.

[0199] Table 5 - Abbreviations

[0200]

[0201]

[0202] Unless otherwise specified, all amounts, ratios and percentages are by weight. The amount of all starting materials in the composition totals 100 weight %. Summary of the invention and description abstract are hereby incorporated by reference. Unless otherwise specified in the context of this specification, the articles "one", "a kind of" and "said" each refer to one (a kind) or more (multiple). Unless otherwise specified, the singular includes plural meanings. The disclosure of the scope includes the scope itself and any value and endpoints contained therein. For example, the disclosure of the scope of 2.0 to 4.0 not only includes the scope of 2.0 to 4.0, but also includes 2.1, 2.3, 3.4, 3.5 and 4.0 and any other numbers contained in the scope individually. In addition, for example, the disclosure of the scope of 2.0 to 4.0 includes subsets such as 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7 and 3.8 to 4.0 and any other subsets contained in the scope. Similarly, disclosure of a Markush group includes the entire group and also includes any individual members and subgroups contained therein. For example, disclosure of the Markush group hydrogen atom, alkyl group, alkenyl group, or aryl group includes the individual member alkyl; the alkyl and aryl subgroups; and any other individual members and subgroups contained therein.

[0203] The term "comprising" and its derivatives, such as "having" and "containing", are used herein in their broadest sense, meaning and encompassing the concepts of "including", "consisting essentially of", and "consisting of". The use of "for example", "for example", "such as", and "including" to list illustrative examples is not meant to be limited to the listed examples. Thus, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to" and encompasses other similar or equivalent examples.

[0204] In general, as used herein, a hyphen "-" or dash "-" within a range of values ​​means "to" or "up to"; ">" means "higher than" or "greater than"; "≥" means "at least" or "greater than or equal to"; "<" means "lower than" or "less than"; and "≤" means "at most" or "less than or equal to". Each of the foregoing patent applications, patents, and / or patent application publications is each expressly incorporated by reference in its entirety in one or more non-limiting embodiments.

[0205] It is to be understood that the appended claims are not limited to individual and particular compounds, compositions, or methods described in the detailed description, which may vary between particular embodiments falling within the scope of the appended claims.

Claims

1. A composition comprising: A) a fluorinated triarylborane Lewis acid selected from the group consisting of: A1) tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct; A2) bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct; A3) bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct; A4) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct; A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane; A6) (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane; A7) bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct; and A8) a combination of two or more of A1) to A7); B) a hydrocarbyloxy-functional organosilicon compound having an average of at least one moiety of the formula -OR 2 A silicon-bonded group wherein each R 2 is an independently selected monovalent hydrocarbon group having 1 to 6 carbon atoms; and C) Silicon-based hydrides having at least one silicon-bonded hydrogen atom per molecule.

2. The composition according to claim 1, wherein A) the fluorinated triarylborane Lewis acid is selected from the group consisting of: A1) tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct; A2) bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct; A3) bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct; A4) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct; A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane; and A7) Bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct.

3. The composition according to claim 2, wherein A) the fluorinated triarylborane Lewis acid is selected from the group consisting of: A1), A2), A3), A4) and A5).

4. The composition of claim 1, wherein A) the fluorinated triarylborane Lewis acid is present in an amount of 0.1 ppm to 5 mol%, based on the combined weight of B) the hydrocarbyloxy functional organosilicon compound and C) the silicon hydride.

5. The composition of claim 4, wherein in step 1), A) the fluorinated triarylborane Lewis acid is present in an amount of 5 ppm to 6,000 ppm based on the combined weight of B) the organosilicon compound and C) the silicon-based hydride.

6. The composition according to any one of claims 1 to 5, wherein B) the organosilicon compound is selected from the group consisting of: B1) Formula R 1 (4-a) S O 2 a Alkoxysilane, wherein each R 1 independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, each R 2 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and subscript a is 1 to 4; and B2) an organosiloxane oligomer or polymer, the organosiloxane oligomer or polymer comprising the formula B2): wherein each D independently represents an oxygen atom, a divalent hydrocarbon group, a divalent siloxane group, or a combination of a divalent hydrocarbon group and a divalent siloxane group; each R X Independent expression -OR 2 A group in which each R 2 As mentioned above; each R 3 independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups; subscript c represents 0, 1, 2 or 3; subscript e represents 0, 1 or 2; and subscript d has a value of 0 or greater, provided that the sum of (e+c) is at least 1, so that on average, at least one R is present in the formula B2) X .

7. The composition of claim 6, wherein the organosiloxane oligomer or polymer comprises a unit formula: (R X R 3 2SiO 1 / 2 ) o (R 3 3SiO 1 / 2 ) p (R 3 2SiO 2 / 2 ) q (R X R 3 SiO 2 / 2 ) r (R X SiO 3 / 2 ) s (R 3 SiO 3 / 2 ) t (SiO 4 / 2 ) u , where R X Represents the above formula -OR 2 The values ​​of the subscripts o, p, q and r are such that o≥0, p≥0, q≥0, r≥0, s≥0, t≥0, u≥0, and the amount (o+r+s) has an average value of 1 or greater.

8. The composition according to any one of claims 1 to 5, wherein C) the silicon-based hydride is selected from the group consisting of: C1) Formula H k S i 5 (4-k) Silane, where each R 5 are independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, and subscript k is 1 to 3; and C2) Unit type (HR 4 2SiO 1 / 2 ) g (R 4 3SiO 1 / 2 ) h (R 4 2SiO 2 / 2 ) i (HR 4 SiO 2 / 2 ) j An organohydrogensiloxane wherein each R 4 is an independently selected monovalent hydrocarbon group containing no aliphatic unsaturation; the values ​​of the subscripts g, h, i and j are such that g ≥ 0, h ≥ 0, the amount (g + h) has an average value of 2, i ≥ 0, j ≥ 0, and the amount (g + j) ≥ 1, and the amount (i + j) ranges from 0 to 1000.

9. The composition according to claim 8, wherein C) the silicon hydride is of the formula HSiR 5 3 silane, wherein each R 5 is an alkyl group having 1 to 6 carbon atoms.

10. The composition according to claim 8, wherein C) the silicon hydride is of the formula A polydiorganohydrogensiloxane wherein the subscript m is 0 or 1 and each R 4 is an alkyl group, and each R 6 Independently selected from H and R 4 The prerequisite is that at least one R 6 It's a hydrogen atom.

11. A method comprising: 1) The starting materials are combined as follows: A) a fluorinated triarylborane Lewis acid selected from the group consisting of: A1) tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct; A2) bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct; A3) bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct; A4) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct; A5) bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane; A6) (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane; A7) bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct; and A8) a combination of two or more of A1) to A7); B) a hydrocarbyloxy-functional organosilicon compound having an average of at least one moiety of the formula -OR 2 A silicon-bonded group wherein each R 2 is an independently selected monovalent hydrocarbon group having 1 to 6 carbon atoms; and C) a silicon-based hydride having at least one silicon-bonded hydrogen atom per molecule; The product of step 1) is thus formed, which comprises the reaction product of the starting materials B) and C) and comprises HR 2 by-product.

12. The method according to claim 11, wherein the method is carried out at a temperature of 5°C to 70°C.

13. The method according to claim 11, further comprising: and neutralizing the residual fluorinated triarylborane Lewis acid in the product of step 1).

14. The method according to any one of claims 11 to 13, further comprising: During and / or after step 1), remove 2 of the by-products.

15. The method according to any one of claims 11 to 13, further comprising: The reaction product is recovered.

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