Compositions and methods for the reaction of organosilicon compounds with silyl hydrides catalyzed by fluorinated arylborane Lewis acids - Patent Application 20070122993

Abstract

The composition and method can be used to prepare various siloxanes. The composition and method use a fluorinated triarylborane Lewis acid, a hydrocarbonoxy-functional organosilicon compound, and a silyl hydride. The fluorinated triarylborane Lewis acid catalyzes the reaction between the hydrocarbonoxy moiety (from the organosilicon compound) and the silicon-bonded hydrogen atom (from the silyl hydride) to form a siloxane bond.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 63 / 043,153, filed June 24, 2020. U.S. Provisional Patent Application No. 63 / 043,153 is incorporated herein by reference.

[0002] FIELD OF THE INVENTION The composition includes a hydrocarbyloxy-functional organosilicon compound, a silyl hydride, and a fluorinated triarylborane Lewis acid. In the method, the fluorinated triarylborane Lewis acid catalyzes the reaction of a hydrocarbyloxy group from the organosilicon compound with a silicon-bonded hydrogen atom from the silyl hydride, thereby forming a siloxane bond in the resulting product. [Background technology]

[0003] The catalysts primarily used 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 drawbacks, such as yellowing of cured siloxane compositions or the formation of black precipitates over time, alternatives to Pt-based catalysts are needed in the industry. Furthermore, Pt-based catalysts can also suffer from the drawback of requiring high temperatures (80°C to 110°C) to achieve sufficient reactivity to catalyze the formation of siloxane bonds. Summary of the Invention

[0004] The composition comprises A) a fluorinated triarylborane Lewis acid, B) a hydrocarbyloxy-functional organosilicon compound, and C) a silyl hydride. The method comprises combining starting materials comprising A) a fluorinated triarylborane, B) a hydrocarbyloxy-functional organosilicon compound, and C) a silyl hydride. DETAILED DESCRIPTION OF THE INVENTION

[0005] The starting material A) in the compositions and methods described herein is a fluorinated triarylborane Lewis acid. The fluorinated triarylborane Lewis acid has the following formula:

[0006] [ka] wherein each R o is an ortho substituent, and each R m is a meta-substituent, and each R p is a para substituent and R L is optional and comprises a functional group or functional polymer group, and the subscript x is 0 or 1. In the above formula, each R o1-6 , each R m1-6 , and each R p1-3 are independently selected from H, F, or CF3, with the proviso that R o1-6 , R m1-6 , and R p1-3 Not all of the can be H at the same time, and R o1-6 , R m1-6 , and R p1-3 Not all of the above can be F at the same time, and R o1-4 When two or more of the groups are CF3, R o5 and R o6 are each independently selected from H or F. L is optional, i.e., R L exists when the subscript x=1, and R L does not exist when the subscript x=0. R L may be a Lewis base that forms a complex with a fluorinated triarylborane Lewis acid, and / or a molecule or moiety that contains at least one electron pair available for forming a coordinate bond with a Lewis acid, and R is described in paragraphs

[0024] to

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

[0007] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , and R o6 may be H. Alternatively, each of R o1 , R o2 , R o3 , and R o4 may be H. Alternatively, each of R o5 and R o6 may each be F.

[0008] Alternatively, R m1 , R m2 , R m3 , R m4 , R m5 , and R m6 Each of R may be CF3. Alternatively, R m1 , R m2 , R m3 , and R m4 Each of R may be CF3. Alternatively, R m5 and R m6 may each be F. Alternatively, R m5 and R m6 may each be H.

[0009] Alternatively, R p1 , R p2 , and R p3 may be H. Alternatively, each of R p1 and R p2 may be H. Alternatively, R p3 may be F. Alternatively, R p3 may be CF3.

[0010] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R o6 , R p1 , R p2 , and R p3may each be H, and R m1 , R m2 , R m3 , R m4 , R m5 , and R m6 Each of may be CF3. Subscript x may be 1. Alternatively, starting material A) may comprise tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct.

[0011] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R o6 , R m5 , R m6 , R p1 , and R p2 may each be H, and R m1 , R m2 , R m3 , R m4 , and R p3 Each of may be CF3. Subscript x may be 1. Alternatively, starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct.

[0012] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 , and R p2 may each be H, and R o5 , R o6 , and R p3 may each be F, and R m1 , R m2 , R m3 , R m4 Each of may be CF. Subscript x may be 1. Alternatively, starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct.

[0013] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 , R p2 , and R p3 may each be H, and R o5 and R o6 may be F, R m1 , R m2 , R m3 , and R m4 Each of may be CF3. Subscript x may be 1. Alternatively, starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct.

[0014] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R m6 , R p1 , R p2 , and R p3 may each 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 include bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane.

[0015] Alternatively, R m1 , R p1 , R o2 , R o3 , R o4 , R p2 , R p3 , R o5 , and R m6 may each be H, and R o1 , R m2 , Rm3 , R m4 , R o6 , and R m5 Each of may be CF. 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.

[0016] Or R o1 , R o2 , R o3 , R o4 , R p1 , and R p2 may each be H, and R o5 , R o6 , R m5 , and R m6 may each be F, and R m1 , R m2 , R m3 , R m4 , and R p3 Each of may be CF3. Subscript x may be 1. Alternatively, starting material A) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct.

[0017] Alternatively, the fluorinated triarylborane Lewis acids are 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, and 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) through A7). Alternatively, starting material A) may be selected from the group consisting of A1), A2), A3), A4), A5), and A7). Alternatively, starting material A) may be selected from the group consisting of A1), A2), A3), A4), and A5). Alternatively, starting material A) may be selected from the group consisting of A1), A2), and A7). Alternatively, starting material A) can be selected from the group consisting of A2) and A5). Alternatively, starting material A) can be selected from the group consisting of A2), A3), A4), and A5).

[0018] Fluorinated triarylborane Lewis acids are known in the art and can be prepared by known methods, for example, the methods disclosed in WO2019 / 055740, particularly in paragraphs

[0052] to

[0096] , by appropriately changing the starting materials.

[0019] The amount of starting material A) will depend on the types and amounts of the other starting materials used, but starting material A) may be present in an amount of 0.1 ppm to 5 mole %, 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, based on the combined weight of starting materials A), B), and C) in the composition.

[0020] Organosilicon Compounds The starting material B) in the compositions and methods described herein is a hydrocarbonoxy-functional organosilicon compound, i.e., a compound of the formula -OR 2 (In the formula, each R 2 is an independently selected monovalent hydrocarbon group having from 1 to 6 carbon atoms). Starting material B) may be a single organosilicon compound or a combination of two or more different organosilicon compounds. 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 iso-butyl), pentyl, and hexyl (including both straight-chain and branched isomers of 5 to 6 carbon atoms), and alkenyl groups such as vinyl, allyl, butenyl, and hexenyl. Alternatively, each R 2 can be an alkyl group. Alternatively, each R 2 may be ethyl or methyl, or alternatively methyl.

[0021] The starting material B) may comprise a hydrocarbonoxysilane and / or an organosiloxane oligomer or polymer. For example, the organosilicon compound may be B1) of formula R 1 (4-a) SiOR 2 a wherein each R 1 are independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, and each R 2is a monovalent hydrocarbon group of 1 to 6 carbon atoms as described above, and the subscript a is 1 to 4. 1 Examples of suitable monovalent hydrocarbon groups for R 2 Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl (including n-propyl and isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and iso-butyl), as described above for R, and alkyl such as pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, undecyl, and octadecyl (and branched isomers thereof), cycloalkyl such as cyclopentyl and cyclohexyl, alkenyl such as vinyl, allyl, butenyl, and hexenyl, and aryl such as phenyl, tolyl, xylyl, naphthyl, benzyl, 1-phenylethyl, and 2-phenylethyl. 1 Examples of monovalent halogenated hydrocarbon groups 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-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl. Alternatively, each R 1 may be a monovalent hydrocarbon group, or an alkyl or aryl group. Alternatively, each R 1 may be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms. Alternatively, each R 1 may be methyl or ethyl, or alternatively methyl.

[0022] The starting material B1) may include an alkoxysilane, such as a monoalkoxysilane (e.g., trialkylalkoxysilane), a dialkoxysilane (e.g., dialkyldialkoxysilane), a trialkoxysilane (e.g., alkyltrialkoxysilane), a tetraalkoxysilane, or a combination 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 made 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.

[0023] Other commercially available alkoxysilanes include XIAMETER™ OFS-6070 silane, XIAMETER™ OFS-6011 silane, XIAMETER™ OFS-6020 silane, XIAMETER™ OFS-6030 silane, DOWSIL™ Z-6062 silane, DOWSIL™ Z-6300 silane, DOWSIL™ Z-6341 silane, XIAMETER™ OFS-6040 silane, DOWSIL™ Z-6023 silane, DOWSIL™ Z-6015 silane, XIAMETER™ OFS-6920 silane, XIAMETER™ OFS-6690 silane, and XIAMETER™ OFS-6076 silane, all of which are commercially available from The Dow Chemical Company and / or its subsidiaries in Midland, Michigan, USA.

[0024] Alternatively, the starting material B) may comprise an organosiloxane oligomer or polymer. The organosiloxane oligomer or polymer may be represented by the formula B2):

[0025] [ka] 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; and each R X are independently the expressions -OR 2 wherein each R 2 is as described above, and each R 3 are independently 1 and wherein the subscript c represents 0, 1, 2, or 3; the subscript e represents 0, 1, or 2; and the subscript d has a value of 0 or greater; provided that on average at least one R xis present in the formula, the sum of (e+c) is at least 1. Alternatively, the subscript d may have a value from 0 to 18. Alternatively, the subscript c may be 1. Alternatively, the subscript c may be 2 or 3. Alternatively, the subscript e may be 0. Alternatively, the subscript d may be 0. Alternatively, the subscript d may be 2 to 5, or 2 to 3.

[0026] 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

[0027] [ka] Alternatively, one example of D may be an oxygen atom, while another example of D is a divalent hydrocarbon group.

[0028] Or, each R x may be independently selected from the group consisting of alkoxy and alkenyloxy groups. Alternatively, each X may be an alkoxy group, such as methoxy or ethoxy.

[0029] Alternatively, each R in the above formula 3 may be independently selected from alkyl groups of 1 to 20 carbon atoms, aryl groups of 6 to 20 carbon atoms, and aralkyl groups of 7 to 20 carbon atoms.

[0030] Alternatively, the subscript b may be 0.

[0031] The organosiloxane oligomer or polymer may contain the group described by formula B2) above in an amount ranging from 0.2 mol % to 10 mol %, alternatively from 0.5 mol % to 5 mol %, alternatively from 0.5 mol % to 2.0 mol %, alternatively from 0.5 mol % to 1.5 mol %, alternatively from 0.6 mol % to 1.2 mol % of the polymer.

[0032] Starting material B) can have a polyorganosiloxane backbone with a linear structure, i.e., a polydiorganosiloxane backbone. When starting material B) has a polydiorganosiloxane backbone, starting material B) can include an alkoxy endblocked polydiorganosiloxane, an alkoxysilylhydrocarbylene endblocked polydiorganosiloxane, or a combination thereof.

[0033] Alternatively, the starting material B) can be a compound of formula B3):

[0034] [ka] wherein R 3 , R X , 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 a polydiorganosiloxane of formula B3) having 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 a polystyrene standard calibration. Alternatively, subscript f may have a value ranging from 1 to 200,000. Alternatively, in formula B3) above, each R 3 may be independently selected from the group consisting of alkyl, alkenyl, and aryl. Alternatively, R 3 The alkyl group in 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 in may be phenyl. Alternatively, in the above formula, each R Xmay be methoxy or ethoxy. Organosiloxane oligomers and polymers of formula B3) can be prepared, for example, as described in U.S. Patent Application Publication No. 2020-0140618 or WO 2019 / 005711 or WO 2019 / 005713.

[0035] Alternatively, the organosiloxane oligomer or polymer may have the unit formula B4): (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 wherein R X is the above formula -OR 2 wherein the subscripts o, p, q, and r have values ​​such that o≧0, p≧0, q≧0, r≧0, s≧0, t≧0, u≧0, the quantity (o+r+s) has an average value of 1 or greater, alternatively 1 to 6, alternatively 1 to 3, alternatively 1 to 2, and each R 3 is R 1 are independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups as described above for unit formula B4). Alternatively, the quantity (o+p+q+r+s+t+u) may be at least 3, alternatively from 3 to 2000. Alternatively, the quantity (q+r) may be 1 to 2,000, alternatively from 1 to 50. Alternatively, the quantity (o+p) may be 0 to 50, alternatively from 0 to 2. Alternatively, 1≧s≧0. Alternatively, 1≧t≧0. Alternatively, the quantity (o+r+s) has an average value of 1 to 6, alternatively from 1 to 3, alternatively from 1 to 2. Alternatively, in the above unit formula B4), each R 3may be selected from the group consisting of alkyl, alkenyl, and aryl. Alternatively, R 3 The alkyl group in 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 in may be phenyl. Alternatively, in the above formula, each R X may be methoxy or ethoxy.

[0036] Alternatively (for example, when o has an average value of 2 and p=r=s=t=u=0), the starting material B) can be represented by formula B5): R 3 2nd Round X SiO-(R 3 2SiO) b -OSiR X R 3 2 polydiorganosiloxanes, wherein each R 3 and each R X is as defined above, and subscript b is ≧1. Alternatively, subscript b may be 1 to 2,000, or 5 to 900, or 5 to 50. 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 (e.g., methyl, ethyl, and propyl), alkenyl (e.g., vinyl, allyl, and hexenyl), and aryl (e.g., phenyl). Alternatively, in Formula B5), each R X may be methoxy or ethoxy. Polydiorganosiloxanes of formula B3), such as methoxy-terminated polydimethylsiloxanes having viscosities of 5-12 cSt, are commercially available from Gelest, Inc., and 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane is commercially available from Millipore Sigma of St. Louis, Missouri, USA.

[0037] Alternatively, the starting material B) may have the unit formula B6):(R 3 SiO 3 / 2 )m (R 3 R X SiO 2 / 2 ) n (R 3 2nd Round X SiO 1 / 2 ) z wherein R 3 and R X are 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, or 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 3 may 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 haloalkyl (e.g., chloromethyl, chloropropyl, and trifluoropropyl). Alternatively, in unit formula B6), each R X may be methoxy or ethoxy. Those skilled in the art will recognize that the alkoxy-functional siloxane resin may further comprise a hydroxyl group. Examples of suitable alkoxy-functional siloxane resins of unit formula B6) include DOWSIL™ 3037, DOWSIL™ 3074, DOWSIL™ 1686, DOWSIL™ CF0189, DOWSIL™ Z-6289, DOWSIL™ US-CF2403 Resin, and DOWSIL™ 2405 Resin, all manufactured by Dow Silicones Corporation of Midland, Michigan, USA.

[0038] Suitable resins for starting material B) and their preparation methods are known in the art. For example, alkoxy-functional organopolysiloxane resins or resin-polymer blends prepared as described in U.S. Patent Nos. 9,670,392, 10,125,225, or WO 2014 / 124389 can be used as starting material B) herein. Starting material B) can include one or more of the compounds described herein.

[0039] C) Silyl hydride The starting material C) in the compositions and methods described herein is a silyl hydride. The term "silyl hydride" refers to a molecule containing at least one silicon-bonded hydrogen atom (SiH) per molecule. Alternatively, the silyl hydride may have two or more SiHs per molecule. As used herein, the silyl hydride is capable of forming a siloxane bond in the presence of A) a fluorinated triarylborane Lewis acid and B) an organosilicon compound as described above. The starting material C) may comprise one silyl hydride or a combination of two or more different silyl hydrides.

[0040] The silyl hydride can be a C1) silane (e.g., having one silicon atom per molecule). Alternatively, the silyl hydride can be an oligomer or polymer. Polymeric silyl hydrides can be linear, branched, or resinous. For example, the silyl hydride can be a C2) polyorganohydrogensiloxane.

[0041] C1) Silane The starting material C1) is a compound of formula H k SiR 5 (4-k) wherein each R 5 is R 1 and the subscript k is 1 to 3, alternatively 1 or 2, alternatively 1. Alternatively, each R 5may be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms. Alternatively, each R 5 may be methyl or ethyl. Alternatively, the starting material C1) may be a compound of formula HSiR 5 3, wherein each R 5 is an alkyl group of 1 to 6 carbon atoms.

[0042] Examples of suitable silanes for starting material C1) are known in the art and commercially available.Suitable silanes include triethylsilane, dimethylethylsilane, diethylmethylsilane, dimethylisopropylsilane, dimethyl-tert-butylsilane, triisopropylsilane, chloromethyldimethylsilane, tripropylsilane, tributylsilane, triisobutylsilane, trihexylsilane, trioctylsilane, cyclohexyldimethylsilane, dimethylphenylsilane, diphenylmethylsilane, triphenylsilane, phenylsilane, bromoundecylsilane, 2-chloroethylsilane, dodecylsilane, n-octadecylsilane, and (tridecafluoro-1,1,2,2-tetrahydrooctyl)silane, which can be obtained from Sigma-Aldrich Inc., St. Louis, Missouri, USA, or Gelest Inc., Morrisville, Pennsylvania, USA.

[0043] C2) Polyorganohydrogensiloxane When polyorganohydrogensiloxanes (C2) are used as starting materials for silylhydrides, the polyorganohydrogensiloxanes may be homopolymers or copolymers. The polyorganohydrogensiloxanes may be linear, branched, or resinous. The silicon-bonded hydrogen atoms in the polyorganohydrogensiloxanes may be terminal, pendant, or both terminal and pendant.

[0044] Polyorganohydrogensiloxane is HR 4 2SiO 1 / 2 , R 43SiO 1 / 2 , H.R. 4 SiO 2 / 2 , R 4 2SiO 2 / 2 , R 4 SiO 3 / 2 , HSiO 3 / 2 , and SiO 4 / 2 In the above units, each R 4 R is an independently selected monovalent hydrocarbon group free of aliphatic unsaturation. 4 Examples of suitable monovalent hydrocarbon groups include, but are not limited to, alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and their branched isomers), cycloalkyl, such as cyclopentyl and cyclohexyl, and aryl, such as phenyl, tolyl, xylyl, naphthyl, benzyl, 1-phenylethyl, and 2-phenylethyl. Alternatively, each R 4 may be an alkyl group or a cycloalkyl group. Alternatively, each R 4 may be an alkyl group such as methyl.

[0045] When the polyorganohydrogensiloxane is linear, i.e., when it is a polydiorganohydrogensiloxane, the polydiorganohydrogensiloxane has the 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 wherein R 4 is as described above, and the subscripts g, h, i, and j have values ​​such that g≧0, h≧0, the quantity (g+h)=2, i≧0, j≧0, and the quantity (g+j)≧1, and the quantity (i+j) may be from 0 to 1000.

[0046] Alternatively, the polydiorganohydrogensiloxane may be of the formula

[0047] [ka] where the subscript m is 0 or 1, and each R 6 is H and R 4 and independently selected from the group consisting of: 6 is a hydrogen atom.

[0048] Suitable polyorganohydrogensiloxanes include: i) pentamethyldisiloxane, ii) bis(trimethylsiloxy)methyl-silane, iii) tetramethyldisiloxane, iv) bis-dimethylhydrogensiloxy-terminated polydimethylsiloxane; v) bis-dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane); vi) bis-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane; vii) bis-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane); viii) bis-trimethylsiloxy-terminated polymethylhydrogensiloxane; ix) H(CH3)2SiO 1 / 2 Units and SiO 4 / 2 a resin consisting essentially of units; and x) is exemplified by a combination of two or more of i) to ix).

[0049] Methods for preparing linear and branched polyorganohydrogensiloxanes suitable for use as starting material C2), such as the hydrolysis and condensation of organohalosilanes, are well known in the art, as exemplified in U.S. Patent Nos. 5,310,843, 4,370,358, 4,707,531, and 4,329,273. Polyorganohydrogensiloxanes are also commercially available, such as those available from Gelest under the trade names DMS-HM15, DMS-H03, DMS-H25, DMS-H31, and DMS-H41.

[0050] D) Solvent Starting material D) is an optional solvent that can be used to facilitate the combination of starting materials A), B), and / or C) in the compositions and methods described herein. Solvents used herein aid in fluidizing the starting materials but do not essentially react with any of these starting materials. The solvent may be selected based on the solubility of the starting materials and the volatility of the solvent. "Solubility" refers to the solvent being sufficient to dissolve and / or disperse the starting materials. "Volatility" refers to the vapor pressure of the solvent. For example, starting material A), a fluorinated triarylborane Lewis acid, can be dissolved in a solvent prior to step 1). Alternatively, starting material B) can be dissolved in a solvent prior to step 1), for example, when starting material B) is a viscous fluid, such as a gum, or a solid at room temperature, such as a resin. Alternatively, starting material C) can be dissolved in a solvent prior to step 1), for example, when starting material C) is a solid at room temperature, such as a resin. The solvent may be used in any amount as selected by one skilled in the art, depending on various factors such as the choice of starting materials A), B), and C), their solubility, etc.

[0051] A suitable solvent may be a hydrocarbon. 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 comprising two or more solvents may be used herein.

[0052] The amount of solvent may vary depending on various factors, such as the type of solvent selected and the amounts and types of other starting materials selected, etc. However, the amount of solvent may range from 0.1% to 99% by weight, or alternatively, from 2% to 50% by weight, based on the total weight of starting materials A), B), and C).

[0053] method The above-described method includes step 1) of combining starting materials including A) a fluorinated triarylborane Lewis acid, B) an organosilicon compound, and C) a silyl hydride as described above. The starting materials may optionally further include D) a solvent, which may 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) may be dissolved in a solvent before mixing with starting material D). Alternatively, the starting materials in step 1) may consist essentially of the above-described starting materials A), B), and C) (and optionally D)). Alternatively, the starting materials in step 1) may consist of the above-described starting materials A), B), and C) (and optionally D)).

[0054] The step of combining the starting materials comprises the step of preparing a compound of formula OR from starting material B). 2 The resulting product of step 1) is the reaction product of starting materials B) and C) (containing siloxane bonds) and HR 2These conditions may include, for example, mixing by any convenient means. Mixing may be carried out using conventional mixing equipment, such as a stirred batch kettle. Alternatively, when the hydrocarbyloxy-functional organosilicon compound selected as starting material B) and / or the silyl hydride selected as starting material C) are viscous or solid (e.g., gums or resins), mixing under shear may be carried out, for example, using an extruder. The composition may be formed, for example, by mixing the starting materials, including A), B), and C), as described above. Starting materials A), B), and C) may be combined at room temperature or below, or may be heated. For example, when heated, temperatures of 50°C to 150°C, or 100°C to 125°C, may be used during mixing. Alternatively, the temperature for combining starting materials A), B), and C) (and, if present, D)) in step 1) may be 5°C to 70°C. Starting materials A), B), and C) (and, if present, D)) may be combined simultaneously. Alternatively, starting materials A) and B) (and D) if present) can be combined to form a mixture, which can then be combined with starting material C) (and further D) if present), e.g., by adding starting material C) (or a solvent solution thereof) to the mixture, e.g., by metering over a period of time or by adding in one or more aliquots.

[0055] The method may optionally further comprise one or more additional steps: step 2) reacting the compound of formula HR produced in step 1) during and / or after step 1). 2 and / or step 3) removing and / or neutralizing any residual fluorinated triarylborane Lewis acid in the product. 2may be removed by any convenient means, such as stripping and / or burning. Removal and / or neutralization may be carried out by adding E) a neutralizing agent to the product, followed by, optionally, filtering the product. Steps 2) and 3) can be carried out in any order. For example, if particulate by-products are present as a result of neutralization, the method may further include step 4) after neutralization, removing particulates such as alumina by any convenient means, for example, filtration.

[0056] Starting Material E) Neutralizing Agent Starting material E) is a neutralizing agent that can optionally be 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 are commercially available, for example, from Millipore Sigma of St. Louis, Missouri, USA. The amount of neutralizing agent depends on various factors, including the amount of starting material A), but starting material E) may 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, alternatively 1:100 to 1:1. Alternatively, when the neutralizing agent is triphenylphosphine or phenylacetylene, the E:A ratio may be 1:1 to 20:1. Alternatively, when the neutralizing agent is alumina, the E:A ratio may be from 100:1 to 1000:1.

[0057] One or more of the above-described process 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, or 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, or alternatively 30°C. Without wishing to be bound by theory, it is believed that carrying out the process, particularly step 1), at a relatively low temperature (e.g., 90°C or less, alternatively 80°C or less, alternatively 70°C or less, or alternatively 50°C or less) may result in improved reaction rate, yield, or both.

[0058] How to use The above-described compositions and methods can be used to prepare siloxanes, intermediates, and / or branched siloxane networks. Alternatively, the above-described 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. [Example]

[0059] These examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention as set forth in the claims. The starting materials listed in Table 1 and in the Reference Examples were used in the examples herein.

[0060] [Table 1]

[0061] Reference Example 1 - General Procedure Unless otherwise noted, all experimental procedures and manipulations of chemicals were performed in a nitrogen-purged glovebox or on a Schlenk line. All bulk reaction solvents (toluene, diethyl ether, hexane, tetrahydrofuran (THF)) were dried by passage through columns of alumina and Q5 reactive scavenger. All other solvents were purchased anhydrous grade from Aldrich and stored over activated 3 Å molecular sieves before use. NMR solvents (CDCl3, CD2Cl2, and CD6D6) obtained from Cambridge Isotope Laboratories, Inc. were either dried over activated 3 Å molecular sieves or, in the case of CD6D6, dried using Na / K alloy. 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 received. n-Butyllithium (solution in hexane) was titrated prior to use using 1.00 M decanol in toluene with 1,10-phenanthroline as the indicator. 1 1 Watson, SC; Eastham, JF “Colored indicators for simple direct titration of magnesium and lithium reagents”, J. Organomet. Chem., 1967, 9, 165-168.

[0062] Multinuclear NMR spectrum ( 1 H, 13 C. 19 F, 29 Si, 11B) were collected on one of the following instruments: a Varian MR-400 or a Varian VNMRS-500. 11 B NMR spectra were collected exclusively on a Varian VNMRS-500. 1 H and 13 C NMR chemical shifts were referenced in parts per million to the residual solvent peak. 1 5.32 ppm for H-CD2Cl2, 7.15 ppm for C6D6, and 7.25 ppm for CDCl3; 13 C -54.00 ppm for CD2Cl2, 128.00 ppm for C6D6, and 77.00 ppm for CDCl3. 11 B NMR chemical shifts are externally referenced to BF3(Et2O) (0 ppm) 19 F NMR chemical shifts were externally referenced to CFCl (0 ppm). Subambient reaction temperatures were measured using an Extech Instruments EasyView™ 10 Dual K model EA 10 thermometer equipped with a fine JKEM sensor PTFE wire K 36INJ, except when dry ice or ice was the only cooling means.

[0063] Reference Example 2 - Synthesis Procedure - Preparation of Starting Materials Lithium (diethyl etherate) (3,5-bis(trifluoromethyl)phenyl) triisopropoxyborate was prepared as follows.

[0064] [ka]

[0065] To a cooled (-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-butyllithium (23.0 mL, 2.61 M in hexanes, 60.03 mmol) with stirring. The reaction mixture was stirred at -78 °C for 3 hours, forming a precipitate. Triisopropyl borate (11.86 g, 63.06 mmol) in ether (20 mL) was slowly added. The reaction mixture was stirred at -78 °C for 1 hour, then warmed to ambient temperature and stirred for 1 hour to give a slightly cloudy solution. The reaction mixture was filtered, and the volatiles were removed under reduced pressure to give a solid. The resulting solid was triturated 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 first isolated as its ether adduct. 1 H NMR (500MHz, THF-d8) δ8.15(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). 19 F NMR (470MHz, THF-d8) δ-63.02. 11 B NMR (160MHz, THF-d8) δ3.84.

[0066] (3,5-bis(trifluoromethyl)phenyl)diisopropoxyborane was prepared as follows.

[0067] [ka]

[0068] 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, 2 M in ether, 24.6 mmol), and a precipitate formed immediately. The reaction mixture was stirred for 2 hours, filtered, and the volatiles were removed under reduced pressure. The resulting residue was extracted with hexane, filtered, and the volatiles were removed under reduced pressure to give the product as an oil. Yield: 5.10 g, 76.1%. 1 H NMR (500MHz, chloroform-d) δ8.01 (d, J=1.9Hz, 2H), 7.89 (dt, J=2.0, 1.0Hz, 1H), 4.59 (hept, J=6.1Hz, 1H), 1.27 (d, J=6.2Hz, 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.

[0069] Lithium(diethyl etherate)bis(3,5-bis(trifluoromethyl)phenyl)diisopropoxyborane was prepared as follows.

[0070] [ka]

[0071] To a cooled (-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-butyllithium (5.30 mL, 2.61 M in hexane, 60.0 mmol) with stirring. The reaction mixture was stirred at -78°C for 1 hour, and a precipitate formed. (3,5-bis(trifluoromethyl)phenyl)diisoproxiborane (4.82 g, 14.1 mmol) in ether (15 mL) was slowly added. The reaction mixture was stirred at -78°C for 1 hour (some solids visible), then warmed to ambient temperature and stirred overnight to give a clear solution. Volatiles were removed under reduced pressure to give a crystalline-appearing 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 formed. The supernatant was decanted and the volatiles removed under reduced pressure to give a colorless crystalline material. Yield: 8.23 ​​g, 93.5%. 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.

[0072] Bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane was prepared as follows.

[0073] [ka]

[0074] To a solution of lithium (diethyl etherato)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, 2 M in ether, 11 mmol), and a precipitate formed immediately. The reaction mixture was stirred for 1 h and the volatiles were removed under reduced pressure. The residue was extracted with hexane, 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 present). 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.

[0075] Synthesis procedure - catalyst preparation Catalyst sample C1, tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct, was prepared as follows.

[0076] Preparation of lithium isopropoxytris(3,5-bis(trifluoromethyl)phenyl)borate

[0077] [ka]

[0078] To a cooled (-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), n-butyllithium (5.00 mL, 2.5 M in hexane, 12.7 mmol) was slowly added dropwise. The reaction mixture was stirred at -78 °C for 1 hour. Isopropoxybis(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 formed crystals, and the crystals were dried under reduced pressure to give 6.74 g. The supernatant solution was concentrated and chilled in the freezer overnight to give a second crop of crystalline material (1.54 g). Total yield: 8.28 g, 75.6%. 1 H NMR (400MHz, benzene-d6) δ8.09(s, 6H), 7.74(s, 3H), 3.71(p, J=6.1Hz, 1H), 2.97(q, J=7.0Hz, 10H), 0.70(t, J=7.1Hz, 15H), 0.67(d, J=6.2Hz, 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.

[0079] Preparation of tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct

[0080] [ka] To a solution of lithium isopropoxytris(3,5-bis(trifluoromethyl)phenyl)borate (6.700 g, 7.75 mmol) in ether (100 mL) was added chlorotrimethylsilane (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 removed under reduced pressure to give the product as a colorless solid, 4.80 g, 95.2%.

[0081] A portion of the solid (4.041 g) was dissolved in ether (100 mL) and THF (5 mL) was added. Volatiles were removed from the reaction mixture under reduced pressure. The residue was extracted with benzene, filtered, and 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%. 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.

[0082] Catalyst sample C2, bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct, was prepared as follows.

[0083] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane

[0084] [ka] To a cooled (-78 °C, CO2(s) / acetone bath) solution of 1-bromo-4-trifluoromethylbenzene (2.750 g, 12.22 mmol) in diethyl ether (200 mL) was slowly added dropwise n-butyllithium (4.70 mL, 2.535 M in hexanes, 11.9 mmol). The reaction mixture was 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) was slowly added. The reaction mixture was allowed to warm to ambient temperature with stirring overnight to give a clear yellow solution with a trace of precipitate. The solvent was removed under reduced pressure to give a thick yellow oil. The oil was rapidly stirred with hexane (100 mL) overnight (some cloudiness occurred). The hexane layer was decanted, filtered, and the volatiles were removed under reduced pressure. The oil layer was extracted again with hexane, and the process was repeated several times. A small amount of oil that did not dissolve was discarded. The volatiles were removed from the filtrate under reduced pressure to give a yellow oil. The oil was dissolved in diethyl ether (100 mL), and trimethylsilyl chloride (1.5 g, 13.8 mmol) was added. A large amount of precipitate formed within 30 minutes. The reaction mixture was stirred overnight. The reaction mixture was filtered, and the volatiles were removed under reduced pressure to give a pasty beige sludge. The NMR spectrum indicated a nearly complete reaction. The product was dissolved in ether, and additional TMSCl was added (0.4 mL). After stirring for several hours, the volatiles were removed under reduced pressure. The residue was extracted with benzene, filtered, and the volatiles were removed under reduced pressure to give a pasty solid. 1 H NMR spectroscopy still showed 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 give the product as a white solid (5.370 g, 68.90%). NMR spectrum of borane-THF complex: 1H 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). 13 C NMR (126 MHz, benzene-d6) δ 149.08, 148.88, 134.18, 133.62 (d, J = 3.8 Hz), 131.11 (q, J = 32.4 Hz), 129.94 (q, J = 32.1 Hz), 125.06 (d, J = 272.1 Hz), 124.92 (q, J = 3.8 Hz), 124.34 (q, J = 272.7 Hz), 121.22 (dt, J = 8.0, 4.0 Hz), 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.

[0085] Catalyst sample C3, bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct, was prepared as follows.

[0086] Preparation of lithium bis(diethyl etherate)bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)-isopropoxyborate

[0087] [ka]

[0088] In an N2-purged glovebox, 2.06 g (9.78 mmol) of 1-bromo-2,4,6-trifluorobenzene was mixed with 80 mL of diethyl ether in a 250 mL Schlenk flask. A Teflon-coated stir bar was added to the colorless solution, and the flask was sealed with a rubber septum before removing it from the glovebox. In a fume hood, the flask was connected to a nitrogen line and placed in a dry ice / acetone bath (-78 °C) for 20 minutes to cool. A 2.5 M solution of n-butyllithium in hexane (4.3 mL, 10.8 mmol) was added to the cooled solution via syringe. The reaction mixture was stirred at -78 °C for 1 hour. A solution of 4.85 g of bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane in 20 mL of diethyl ether was prepared in the glovebox and drawn up into a syringe. The solution was poured into a flask containing the cold aryllithium solution at -78 °C, and the mixture was stirred at this temperature for 30 min. The dry ice / acetone bath was removed, and the reaction mixture was allowed to slowly warm to room temperature with stirring overnight. The next morning, all volatiles were removed under vacuum to yield a sticky yellow solid. The flask was returned to the glovebox, and the sticky yellow material was extracted with 1) 80 mL of pentane, 2) 80 mL of hexane, and 3) 60 mL of a 50 / 50 ether / hexane mixture. All three solutions were placed in the glovebox freezer overnight (-40 °C), causing a white crystalline material to precipitate from solution. The crystalline material was collected by filtration, washed with cold pentane (-40 °C), and dried under vacuum for 1 h. Total yield: 5.29 g (impure, approximately 5.5 mmol of the desired lithium salt, 56%). Note that pure material was not obtained. The lithium salt was contaminated with the isopropoxyborane starting material (12%–22% contamination, depending on the batch of solid material recovered). It was decided to carry the isolated material forward to the next step in the reaction without further purification. 1H NMR (400MHz, benzene-d6) δ8.26 (s, 4H, ortho-ArCH), 7.80 (s, 2H, para-ArCH), 6.22-6.07 (m, 2H, ortho-ArCH), 3.68 (hept, J=5.8Hz, 1H, CH(CH3)2), 3.07(q, J=7.1Hz, 8H, OCH2), 0.81(t, J=7.1Hz, 12H, OCH2CH3), 0.67(d, J=6.2Hz, 6H, CH(CH3)2). 13 C 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, ortho-ArCH), 130.7(q, J=31.9Hz, ArC-CF3), 125.5(q, J=272.4Hz, CF3), 119.9(p, J=4.0Hz, para-ArCH), 10 1.0(ddd, J=36.6, 24.0, 3.7Hz, meta-ArCH), 65.9(s, OCH(CH3)2), 65.8(s, OCH2CH3), 25.7(s, OCH(CH3)2), 14.7(s, OCH2CH3). 19 F NMR (376MHz, benzene-d6) δ -62.7 (s, 12F, CF3), -104.4 (br s, 2F, ortho-ArF), -112.3 (m, 1F, para-ArF).

[0089] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoroborane)

[0090] [ka]

[0091] In an N2-purged glovebox, 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: The lithium borate salt was contaminated with 22% bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane). Trimethylsilyl chloride (1.0 mL, 7.9 mmol) was added to the room temperature solution with stirring. There was no immediate sign of reaction. The mixture was stirred at room temperature overnight. The next morning, a large amount of LiCl precipitate had formed in the flask. An aliquot of the reaction mixture was removed and 19 Analysis by F NMR spectroscopy confirmed the reaction was complete. The reaction mixture was filtered through Celite to remove LiCl, and the filtrate was pumped to dryness. The resulting sticky white solid was extracted with 80–90 mL of hexane and filtered again. The hexane solution was placed in a glovebox freezer overnight (−40 °C), during which time a white microcrystalline solid precipitated. The solid was collected by filtration, washed with 5–10 mL of cold pentane (−40 °C), and dried under vacuum for 1 h. Multinuclear NMR spectroscopy confirmed the formation of the desired material in pure form. Yield: 0.992 g, 1.75 mmol, 53.2%. 1 H NMR (400 MHz, benzene-d6) δ 7.88 (s, 6H, ArCH on CF3-substituted ring), 6.03 (m, 2H, ArCH on 2,4,6-trifluorophenyl ring). 13 C NMR (101MHz, benzene-d6) δ167.4 (dt, J=257.6, 16.2Hz, para-ArCF), 166.2 (dt, J=253.5, 15.2Hz, ortho-ArCF), 142.8 (br s, ArC), 137.5(d, J=3.0Hz, ortho-ArCH), 132.1(q, J=33.4Hz, ArC-CF3), 126.9(pent, J=4.0Hz, para-ArCH), 124.1(q, J=273.0Hz, CF3), 112.6(br s, ArC), 101.6(ddd, J=29.0, 24.9, 3.7Hz, meta-ArCH). 19F NMR (376MHz, benzene-d6) δ -63.1 (s, 12F, CF3), -92.4 (m, 2F, ortho-ArCF), -98.5 (s, 1F, para-ArCF). 11 B NMR (160 MHz, benzene-d6) δ 62.9 (broad s).

[0092] Preparation of the THF adduct of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoroborane)

[0093] [ka]

[0094] In an N2-purged glovebox, 0.992 g (1.75 mmol) of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane was weighed into a 110 mL glass vial and dissolved in 50 mL of THF. The THF was removed under vacuum with stirring to give a white solid. The solid was triturated with 40 mL of pentane to aid in the removal of 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-trifluorophenyl)borane. Yield: 0.969 g, 1.51 mmol, 86.3%. 1 H NMR (400MHz, benzene-d6) δ7.96 (s, 4H, ortho-ArCH), 7.79 (s, 2H, para-ArCH), 6.16 (t, J=8.0Hz, 2H, meta-ArCH), 3.10 (m, 4H, OCH2), 0.79 (m, 4H, CH2). 13C NMR (101MHz, benzene-d6) δ165.3 (ddd, J=245.4, 17.7, 14.3Hz, ortho-ArCF), 163.9 (dd, J=249.5, 16.2Hz, para-ArCF), 148.4 (br s, ArC), 134.0(s, ortho-ArCH), 131.4(q, J=32.4Hz, ArC-CF3), 121.8(m, para-ArCH), 124.8(q , J=272.7Hz, CF3), 101.3(ddd, J=32.8, 24.2, 3.2Hz, meta-ArCH), 72.6(s, OCH2), 24.8(s, CH2). 19 F NMR (376MHz, benzene-d6) δ -62.8 (s, 12F, CF3), -96.9 (s, 2F, ortho-ArCF), -108.5 (s, 1F, para-ArCF). 11 B NMR (160 MHz, benzene-d6) δ 13.2 (broad s).

[0095] Catalyst sample C4, bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl) THF adduct, was prepared as follows.

[0096] Preparation of lithium bis(diethyl etherate)bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)isopropoxyborate

[0097] [ka]

[0098] To a cooled (-78 °C, CO2(s) bath) solution of 1-bromo-2,6-difluorobenzene (1.46 g, 7.56 mmol) in diethyl ether (100 mL) was slowly added dropwise n-butyllithium (3.00 mL, 2.48 M in hexanes, 7.44 mmol). The reaction mixture was stirred at -78 °C for 1 h, and then a solution of bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane (3.69 g, 7.44 mmol) in ether (10 mL) was slowly added. A precipitate formed while the reaction mixture was warmed to ambient temperature. By the time the reaction mixture reached room temperature, the precipitate had dissolved, giving a clear solution, which was stirred for several hours. The solution was filtered, and the volatiles were removed under reduced pressure to give a crystalline-appearing solid. The solid was dissolved in minimal boiling ether, and the solution was placed in a glovebox freezer (-33 °C). After cooling overnight, the supernatant was decanted from the crystals that had formed. The crystals were dried under vacuum. Yield: 6.85 g, 88.4%. 1 H 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, 2 H), 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), 131.28(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).

[0099] Preparation of the THF adduct of bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane

[0100] [ka]

[0101] Lithium bis(diethyletherato)bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)isopropoxyborate (5.85 g, 10.6 mmol) was dissolved in ether (150 mL) and chlorotrimethylsilane (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 stirred over the weekend. By Monday, the volatiles had evaporated (unsealed container). The colorless solid was extracted with ether and filtered. The volatiles were removed under reduced pressure to give the product as a colorless solid, 4.98 g. The NMR spectrum indicated pure borane, but only about 86% of the ether required for the monoetherate complex. The product was dissolved in ether to give a cloudy solution. THF (6 mL) was added, and the solution became clear. The volatiles were removed under reduced pressure to give a glassy solid. The residue was extracted with benzene, filtered and the volatiles removed under reduced pressure to give a white solid. Yield: 4.63 g, 69.9%. 1 H NMR (400MHz, benzene-d6) δ8.02 (d, J=1.8Hz, 2H), 7.77 (dq, J=1.9, 0.9Hz, 1H), 6. 71-6.60(m, 0H), 6.48(t, J=8.4Hz, 1H), 3.17-3.09(m, 2H), 0.77-0.68(m, 2H). 13 C 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). 19F 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).

[0102] Catalyst sample C5, bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane, was prepared as follows.

[0103] Preparation of lithium isopropoxybis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate

[0104] [ka] To a cooled (-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), n-butyllithium (4.00 mL, 2.535 M in hexane, 10.14 mmol) was slowly added dropwise. The reaction mixture was stirred at -78 °C for 1 hour. Isopropoxybis(3,5-bis(trifluoromethyl)phenyl)borane (5.036 g, 10.15 mmol) in 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 with stirring overnight, giving a pale yellow, clear solution. The reaction mixture was stripped of volatiles to give a yellow oil. The oil was extracted with benzene. No insoluble material was found. The reaction mixture was stripped of volatiles to give a yellow oil. The yield was 7.88 g, 98.3%. 1 H 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). 13C NMR (101MHz, benzene-d6) δ158.31, 153.97, 135.44(q, J=3.7Hz), 135.23, 133.55(t, J=4.1Hz), 133.25, 133.18, 132.37(d, J=97.8Hz), 130.92(q, J=32. 0Hz), 127.80(q, J=273.9Hz), 124.92(q, J=272.5Hz), 124.66(q, J=272.8H z), 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.

[0105] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane

[0106] [ka] Lithium (diethyl etherato)isopropoxy-bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)-borate (7.88 g, 9.97 mmol) was dissolved in ether (150 mL). Chlorotrimethylsilane (2.6 mL, 20.5 mmol) was added. The reaction mixture was stirred overnight to give a yellow solution with a colorless precipitate. The 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%. THF-free compounds: 1 H 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). 13C 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 B NMR (160 MHz, benzene-d6) δ 64.37.

[0107] Catalyst sample C6, (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane, was prepared as follows.

[0108] Preparation of lithium diisopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate

[0109] [ka] n-Butyllithium (4.00 mL, 2.535 M in hexane, 10.14 mmol) was added with stirring to a cooled (-101 °C to -99 °C, CO2(s), then N2(l), methanol bath) solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (3.000 g, 10.24 mmol) in diethyl ether (150 mL). The reaction mixture was stirred at approximately -100 °C for 2 h and then warmed to -78 °C. Bis(isopropoxy)(3,5-bis(trifluoromethyl)phenyl)borane (3.510 g, 10.26 mmol) in ether (10 mL) was slowly added. The reaction mixture was allowed to warm to ambient temperature with stirring overnight. Volatiles were removed under reduced pressure from the pale yellow, nearly clear solution to give a crystalline-looking solid. The solid was dissolved in ether (10 mL) and placed in the freezer. No precipitate was observed. 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 crop: 3.318 g. NMR analysis of the crystals showed pure desired compound. The supernatant was placed in the freezer overnight. A crystalline material formed. The supernatant was removed with a pipette and discarded. The crystalline residue was dried under reduced pressure: 2.017 g. Total yield: 5.335 g, 82.79%. 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. 8Hz, 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). 13C NMR (101MHz, benzene-d6) δ153.10, 136.65(q, J=29.6Hz), 134.81(dd, J=2.7Hz, 1 .9Hz), 133.93(q, J=3.6Hz), 131.93(q, J=31.6Hz), 131.35, 129.76(q, J=31.9 Hz), 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. 19 F NMR (376 MHz, benzene-d6) δ -55.79, -62.66, -63.30. 11 B NMR (160 MHz, benzene-d6) δ 5.32.

[0110] Preparation of isopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane

[0111] [ka] To a solution of lithium (diethyl etherate)diisopropoxy-(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate (3.318 g, 5.21 mmol) in ether (10 mL) was added chlorotrimethylsilane (2.0 mL), causing a precipitate to rapidly form. The reaction mixture was stirred overnight. The reaction mixture was filtered, and the volatiles were removed under reduced pressure. NMR analysis indicated the reaction was complete. Some presumed TMS-O-iPr ether was also present. A second crop of lithium diisopropoxy(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate, prepared as above, was treated similarly (lithium salt 2.017 g, 3.17 mmol, 0.2 mL of TMSCl) and stirred for 3 h. Total 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. The volatiles were removed under reduced pressure. The residue was extracted with hexane, 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%. 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). 13 C 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. 19F 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.

[0112] Preparation of lithium isopropoxybis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borate

[0113] [ka] To a cooled (-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), n-butyllithium (2.40 mL, 2.535 M in hexane, 6.08 mmol) was slowly added dropwise. 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 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 overnight with stirring, resulting in a pale yellow, clear solution. The reaction mixture was stripped of volatiles to give a yellow oil. The oil was extracted with benzene. No insoluble material was found. The reaction mixture was stripped of volatiles to give a yellow oil. The yield was 4.21 g, 87.6%. 1 H 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). 13C NMR (101 MHz, benzene-d6) δ 157.17, 156.73, 134.42, 133.88 (q, J = 3.6 Hz), 133.04 (d, J = 28.4 Hz), 132.88 (q, J = 32.1 Hz), 129.95 (q, J = 31.9 Hz), 127.74 (q, J = 273.6 Hz), 127.33 (q, J = 6.9 Hz), 124.97 (q, J = 272.4 Hz), 124.50 (q, J = 273.0 Hz), 122.72 (q, J = 3.8 Hz), 118.78 (p, J = 4.1 Hz), 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.

[0114] Preparation of bis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borane

[0115] [ka] To a solution of lithium (diethyl etherato)isopropoxybis(2,5-bis(trifluoromethyl)phenyl)(3,5-bis(trifluoromethyl)phenyl)borate (3.915 g, 4.95 mmol) in diethyl ether (150 mL) was added chlorotrimethylsilane (1.10 mL, 10.1 mmol) with stirring. A precipitate formed in the solution within 15 minutes. The reaction mixture was stirred overnight. The mixture was filtered and the volatiles removed under reduced pressure to give 3.260 g of a colorless solid. The product was extracted with hexane, filtered, and the volatiles removed under reduced pressure to give the product as a pale solid, 3.109 g, 96.53% yield. 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). 13C NMR (126 MHz, benzene-d6) δ 141.54, 140.05, 138.35 (q, J = 3.8 Hz), 135.84 (q, J = 32.0 Hz), 133.02 (q, J = 33.0 Hz), 132.02 (q, J = 33.7 Hz), 129.98 (q, J = 3.5 Hz), 128.29, 127.91 (d, J = 2.4 Hz), 127.13 (q, J = 4.2 Hz), 124.15 (q, J = 274.2 Hz), 123.70 (q, J = 273.2 Hz), 123.37 (q, J = 273.2 Hz). 19 F NMR (470 MHz, benzene-d6) δ -56.40, -63.31, -63.58. 11 B NMR (160 MHz, benzene-d6) δ 67.58.

[0116] Catalyst sample C7 was prepared as follows.

[0117] Preparation of tris(2,5-bis(trifluoromethyl)phenyl)borane

[0118] [ka] This reaction was carried out similarly to previously reported procedures. 2Isopropylmagnesium chloride-lithium chloride (46.0 mL, 58.0 mmol, 1.26 M solution 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 h. The reaction mixture was cooled to -78 °C and boron trifluoride diethyl etherate (2.43 mL, 2.74 g, 19.3 mmol) in 15 mL of ether was added. The reaction mixture was allowed to warm to room temperature with stirring over the weekend. The volatiles were removed from the solution to give 12.77 g of a reddish solid. The residue was extracted with toluene and filtered. The volatiles were removed under reduced pressure to give 10.75 g of a pink powder. The solid was extracted with methylene chloride to give a light purple solution. The solution was placed in the freezer overnight. The supernatant was decanted from the very light pinkish crystalline material that formed. The material was dried under vacuum. Yield: 7.0003 g, 55.73%. 2 Herrington, TJ, Thom, AJW, White, AJP, Ashley, AEDalton Trans, 2012,41,9019. TH-free products: 1 H 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 (101 MHz, benzene-d6) δ 141.10, 136.50 (q, J = 32.2 Hz), 132.81 (q, J = 33.1 Hz), 131.59 (q, J = 3.8 Hz), 128.85 (q, J = 3.7 Hz), 127.45 (q, J = 3.4, 2.1 Hz), 123.93 (q, J = 274.6 Hz), 123.59 (q, J = 273.1 Hz). 19 F NMR (376 MHz, benzene-d6) δ -56.48, -63.77. 11 B NMR (160 MHz, benzene-d6) δ 68.81.

[0119] Catalyst sample C8, bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct, was prepared as follows.

[0120] Preparation of lithium (tetrahydrofuranate) bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)isopropoxyborate

[0121] [ka] n-Butyllithium (3.00 mL, 2.54 M in hexane, 7.61 mmol) was added with stirring to a cooled (-101 °C to -99 °C, CO2(s), then N2(l), methanol bath) solution of 1-bromo-2,3,5,6-tetrafluoro-4-trifluoromethylbenzene (2.26 g, 7.61 mmol) in diethyl ether (100 mL). The reaction mixture was stirred at -100 °C for 2 h and then warmed to -76 °C. Bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane (3.78 g, 7.61 mmol) in ether (10 mL) was slowly added to the reaction mixture. The reaction mixture was allowed to warm slowly to ambient temperature with stirring overnight. The next day, the pale yellow, nearly clear solution was filtered, and the volatiles were removed from the filtrate under reduced pressure to give a crystalline-appearing solid. The solid was washed with hexane, filtered, and dried under reduced pressure. An aliquot of the solid was removed for NMR analysis. The solid aliquot had limited solubility in benzene. The aliquot was dissolved in THF, the volatiles removed under reduced pressure, and then re-analyzed by NMR in benzene. Yield: 6.16 g, 93.2%. 1 H NMR (500MHz, benzene-d6) δ8.32(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). 13C NMR (126MHz, benzene-d6) δ144.07(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 -123.43(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.

[0122] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane tetrahydrofuranate, THF adduct

[0123] [ka] To a solution of lithium (tetrahydrofuranate) 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 chlorotrimethylsilane (2.00 mL, 18.4 mmol) with stirring. The reaction mixture was stirred overnight. The next day, 19 Analysis of an aliquot of the reaction mixture by F NMR spectroscopy revealed that no reaction had occurred. A solution of hydrogen chloride in ether (7.00 mL, 2.0 M, 14.0 mmol) was added and the reaction mixture was stirred overnight. The next day, 19Analysis of an aliquot of the reaction mixture by F NMR spectroscopy 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 that was dried under reduced pressure. NMR analysis of the powder revealed that one molecule of isopropanol remained in the coordination sphere of the borane. Yield as the isopropanol adduct of borane: 2.45 g, 52.8%.

[0124] A portion of the 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 yield large crystals. The supernatant was removed, and the very pale 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 the borane isopropanol adduct. The THF did not displace the coordinated alcohol. The supernatant solution and hexane washes from the crystals were combined and concentrated under vacuum to yield a second crop of crystals (0.422 g). The second crop of crystals was washed and dried in the same manner as the first crop. NMR analysis indicated the presence of coordinated isopropanol but little or no THF. THF was added, and then the volatiles were removed under reduced pressure. NMR analysis indicated the presence of THF, but still some isopropanol. The solid was dissolved in THF and then removed by pumping. This was repeated five more times to give the THF adduct of the product as a white powder. Yield: 0.413 g, 22.4%. THF adduct: 1 H NMR (400 MHz, benzene-d6) δ 7.87 (s, 4H), 7.80 (s, 4H), 3.02-2.93 (m, 4H), 0.78-0.72 (m, 4H). 13C 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 .44, 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. 19 F NMR (376MHz, benzene-d6) δ -56.57 (t, J=21.0Hz), -62.95, -130.60 (dd, J=22.5, 13.2Hz), -140.71 (qt, J=19.7, 8.6Hz). 11 B NMR (160 MHz, benzene-d6) δ 7.22.

[0125] The catalyst samples prepared as described above in Reference Example 2 are shown below.

[0126] [ka]

[0127] The structures of fluorinated arylborane Lewis acid catalyst samples C1-C8 and a commercially available FAB are shown above. Structure C1 is tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct (corresponding to claimed starting material A1). Structure C2 is bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct (corresponding to claimed starting material A2). Structure C3 is bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct (corresponding to claimed starting material A3). Structure C4 is bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct (corresponding to claimed starting material A4). Structure C5 is bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane (corresponding to the claimed starting material A5). Structure C6 is (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane (corresponding to the claimed starting material A6). 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 claimed starting material A7).

[0128] Reference Example 3 - General Procedure HTMS, PMDS, TES, TMSOMe, and FAB (listed above in Table 1) were used as received. In a nitrogen-purged glovebox, a solution of a fluorinated triarylborane Lewis acid sample (catalyst) was prepared in a 10 mL glass vial (e.g., 30.7 mg, 0.06 mmol of FAB was dissolved in 5 mL of anhydrous deuterated benzene). An NMR tube was charged with a silyl hydride (e.g., HTMS, 32.6 μL, 0.12 mmol, 1 equiv.), an organosilicon compound with an alkoxy group (e.g., trimethylmethoxysilane, 17 μL, 0.12 mmol, 1 equiv.), and an internal standard (mesitylene, 16.8 μL, 0.12 mmol, 1 equiv.). The catalyst (0.5 mL, 0.006 mmol, 5 mol%) was delivered as a stock solution via pipette. The final concentration of the solution was 0.24 M. The tube was capped and 1 H NMR spectra were measured at regular time intervals, and conversion was established by comparison with an internal standard using 400 MHz NMR.

[0129] All fluorinated triarylborane Lewis acid samples tested catalyzed the SiH-SiOR curing reaction under the conditions tested, except for C7. Without wishing to be bound by theory, it is believed that C7 was too sterically bulky to catalyze this reaction under these conditions, further demonstrating that not all fluorinated arylboranes catalyze this reaction.

[0130] [ka]

[0131] Reaction schemes using various silyl hydrides and fluorinated triarylboranes.

[0132] [Table 2]

[0133] Without wishing to be bound by theory, it is believed that TES is more difficult to react than HMTS, which is more difficult to react than PMDS, and C6 results in higher conversions at higher temperatures.

[0134] Industrial Applicability The compositions and methods described herein use fluorinated triarylborane Lewis acids as catalysts. These fluorinated triarylborane Lewis acids provide better reaction rate control than FAB. The compositions and methods described herein offer the additional advantage that the order of addition of the starting materials is not important; the starting materials can be combined in any order. The compositions and methods may provide advantages in pot life and / or process robustness. Without wishing to be bound by theory, it is believed that silyl hydrides should not be mixed with FAB because this would cause self-curing.

[0135] Definitions and Use of Terms The abbreviations used herein have the definitions in Table 5 below.

[0136] [Table 3]

[0137] All amounts, ratios, and percentages are by weight unless otherwise indicated. The amounts of all starting materials in a composition total 100% by weight. The Summary and Abstract are incorporated herein by reference. The articles "a," "an," and "the" each refer to one or more, unless otherwise indicated by the context of the specification. The singular includes the plural unless otherwise indicated. The disclosure of a range includes the range itself and any subsumed within the range, as well as the endpoints. For example, the disclosure of a range of 2.0 to 4.0 includes not only the range 2.0 to 4.0, but also 2.1, 2.3, 3.4, 3.5, and 4.0 individually, and any other number subsumed within the range. Further, for example, disclosure of a range of 2.0 to 4.0 also includes the subsets, for example, 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7, and 3.8 to 4.0, as well as any other subset subsumed within that range. Similarly, disclosure of a Markush group includes the group as a whole, as well as any individual members and subgroups subsumed therein. For example, disclosure of the Markush group "hydrogen atom, alkyl group, alkenyl group, or aryl group" includes the individual members alkyl, the subgroups alkyl and aryl, and any other individual members and subgroups subsumed within the Markush group.

[0138] The term "comprising" and its derivatives, such as "comprise" and "comprises," are used herein in their broadest sense to mean and encompass the concepts of "including," "include," "consisting essentially of," and "consisting of." The use of "for example," "eg," "such as," and "including" to list examples does not limit the examples listed. 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.

[0139] Generally, as used herein, a hyphen "-" or a wavy line "~" in a range of values ​​means "to" or "through," ">" means "above" or "greater-than," "≥" means "at least" or "greater-than or equal to," "<" means "below" or "less-than," and "≤" means "at most" or "less-than or equal to." Each of the foregoing patent applications, patents, and / or patent publications is expressly incorporated herein by reference in its entirety on an individual basis in one or more non-limiting embodiments.

[0140] It is to be understood that the appended claims are not limited to the specific compounds, compositions, or methods described therein for purposes of describing the Detailed Description of the Invention, and that variations may occur among specific embodiments within the scope of the appended claims.

Claims

1. 1. A composition comprising: A) a fluorinated triarylborane Lewis acid, 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, A7) bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct, and A8) a fluorinated triarylborane Lewis acid selected from the group consisting of a combination of two or more of A1) to A5 and A7); B) Formula -OR ２ [In the formula, each R ２ is an independently selected monovalent hydrocarbon radical of 1 to 6 carbon atoms; and C) a silyl hydride having at least one silicon-bonded hydrogen atom per molecule.

2. A) is 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 described in claim 2, wherein A) is selected from the group consisting of A1), A2), A3), A4), and A5).

4. A composition described in any one of claims 1 to 3, wherein A) is present in an amount of 0.1 ppm to 5 mol % based on the total weight of B) the hydrocarbonoxy-functional organosilicon compound and C) the silyl hydride.

5. The composition described in claim 4, wherein A) 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 silyl hydride.

6. B) The organosilicon compound is B1) Formula R １ （４－ａ） SiOR ２ ａ [In the formula, each R １ are independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, and each R ２ is a monovalent hydrocarbon radical of 1 to 6 carbon atoms, and the subscript a is 1 to 4; and B2) Formula B2) 【Chemical 1】 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; Ｘ are independently represented by the formula -OR ２ (In the formula, each R ２ is as defined above), and each R ３ are 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 on average at least one R ｘ wherein the sum of (e+c) is at least 1.

7. The organosiloxane oligomer or polymer may have the unit formula (R Ｘ R ３ ２ SiO １／２ ) ｏ (R ３ ３ SiO １／２ ) ｐ (R ３ ２ SiO 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 [In the formula, R Ｘ is the above formula -OR ２ wherein the subscripts o, p, q, and r have values ​​such that o≧0, p≧0, q≧0, r≧0, s≧0, t≧0, u≧0, and the quantity (o+r+s) has an average value of 1 or greater.

8. C) The silyl hydride is C1) Formula H ｋ SiR ５ （４－ｋ） [In the formula, each R ５ are independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, and the subscript k is 1 to 3; and C2) Unit formula (HR) ４ ２ SiO １／２ ) ｇ (R ４ ３ SiO １／２ ) ｈ (R ４ ２ SiO ２／２ ) ｉ (HR ４ SiO ２／２ ) ｊ [In the formula, each R ４ are independently selected monovalent hydrocarbon radicals free of aliphatic unsaturation, and the subscripts g, h, i, and j have values ​​such that g≧0, h≧0, the quantity (g+h) has an average value of 2, i≧0, j≧0, and the quantity (g+j)≧1, and the quantity (i+j) ranges from 0 to 1000. C) is a compound of the formula HSiR ５ ３ [In the formula, each R ５ is an alkyl group of 1 to 6 carbon atoms.

10. C) is a compound of the formula 【Chemistry 2】 wherein the subscript m is 0 or 1, and each R ４ is an alkyl group, and each R ６ is H and R ４ and independently selected from the group consisting of: ６ The composition of claim 8, wherein the polydiorganohydrogensiloxane is a polydiorganohydrogensiloxane of the formula:

11. 1. A method comprising: １） A) a fluorinated triarylborane Lewis acid, 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, A7) bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct, and A8) a fluorinated triarylborane Lewis acid selected from the group consisting of a combination of two or more of A1) to A5 and A7); B) Formula -OR ２ [In the formula, each R ２ is an independently selected monovalent hydrocarbon radical of 1 to 6 carbon atoms; and C) a silyl hydride having at least one silicon-bonded hydrogen atom per molecule, to form a silyl hydride having at least one silicon-bonded hydrogen atom per molecule, the reaction product of starting materials B) and C) and HR ２ and a by-product comprising:

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

13. 13. The method of claim 11 or 12, further comprising the step of neutralizing any residual fluorinated triarylborane Lewis acid in the product of step 1).

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

15. 15. The method of any one of claims 11 to 14, further comprising recovering the reaction product.

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