BEDARD ANNE-CATHERINE (US)
SPINNEY HEATHER (US)
WILSON DAVID (US)
RAGHURAMAN ARJUN (US)
MUKHOPADHYAY SUKRIT (US)
SHAH ANDREW (US)
DEVORE DAVID (US)
LAITAR DAVID (US)
REDDEL JORDAN (US)
LAI SHUQI (US)
DOW GLOBAL TECHNOLOGIES LLC (US)
WO2020131365A1 | 2020-06-25 | |||
WO2020247334A1 | 2020-12-10 | |||
WO2019023008A1 | 2019-01-31 | |||
WO2002012386A1 | 2002-02-14 | |||
WO2019055740A1 | 2019-03-21 | |||
WO2019082992A1 | 2019-05-02 | |||
WO2019182986A1 | 2019-09-26 | |||
WO2019182993A1 | 2019-09-26 |
US5310843A | 1994-05-10 | |||
US4370358A | 1983-01-25 | |||
US4707531A | 1987-11-17 | |||
US4329273A | 1982-05-11 | |||
US6624254B1 | 2003-09-23 | |||
US201862644635P | 2018-03-19 | |||
US201862644624P | 2018-03-19 | |||
US201862644808P | 2018-03-19 |
Claims: 1. A composition comprising: A) a fluorinated triarylborane Lewis acid of formula ; where each of Ro1, Ro2, Ro3, Ro4, Ro5, Ro6, Rm1, Rm2, Rm3, Rm4, Rm5, Rm6, Rp1, Rp2, and Rp3 is independently selected from H, F, or CF3; R includes a functional group or a functional polymer group; and subscript x is 0 or 1; with the provisos that: not all of Ro1, Ro2, Ro3, Ro4, Ro5, Ro6, Rm1, Rm2, Rm3, Rm4, Rm5, Rm6, Rp1, Rp2, and Rp3 can be F simultaneously; not all of Ro1, Ro2, Ro3, Ro4, Ro5, Ro6, Rm1, Rm2, Rm3, Rm4, Rm5, Rm6, Rp1, Rp2, and Rp3 can be H simultaneously; and when two or more of Ro1, Ro2, Ro3, and Ro4 are CF3, then Ro5 and Ro6 are each selected from H or F; and B) a silyl hydride having at least one silicon-bonded hydrogen atom per molecule. 2. The composition of claim 1, where starting material A) 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; 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). 3. The composition of claim 1 or claim 2, where B) the silyl hydride is selected from the group consisting of: B1) a silane of formula HkSiR5(4-k), where each R5 is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, and subscript k is 1 to 3; B2) a polyorganohydrogensiloxane comprising two or more siloxane units selected from the group consisting of HR42SiO1/2, R43SiO1/2, HR4SiO2/2, R42SiO2/2, R4SiO3/2, HSiO3/2 and SiO4/2, where each R4 is an independently selected monovalent hydrocarbon group, which is free of aliphatic unsaturation; and B3) a polyolefin having a silicon-bonded hydrogen functional group of formula (B3-1): , where each R1 is an independently selected monovalent hydrocarbon group and each subscript a is independently 1 or 2. 4. The composition of claim 3, where starting material B1) is a silane of formula HSiR53, where each R5 is an alkyl group of 1 to 6 carbon atoms; starting material B2) is a polydiorganohydrogensiloxane of unit formula: (HR42SiO1/2)g(R43SiO1/2)h(R42SiO2/2)i(HR4SiO2/2)j, where R4 is as described above, and subscripts g, h, i, and j have values such that g ≥ 0, h ≥ 0, a quantity (g + h) has an average value of 2, i ≥ 0, j ≥ 0, and a quantity (g + j) ≥ 1, and a quantity (i + j) ranges from 0 to 1000; and starting material B3) is an SiH-functional polyolefin selected from the group consisting of unit formula (B3-2): , where R1 and subscript a are as described above, each D1 is independently a divalent hydrocarbon group of 2 to 50 carbon atoms, each R25 is independently H, a monovalent hydrocarbon group of 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms, and subscripts M and N have values such that 1 ≤ M ≤ 10, and 10 ≤ N ≤ 20,000. unit formula (B3-3): Hf[(Ret)t(RO)u]g[ (2-f), where subscript a and R1 are as described above, subscript f is 0 or 1, subscripts t and u are fractions with relative values such that 0 < t ≤ 1, 0 ≤ u ≤ 1, subscript g is 1 or more, each Ret represents an ethylene unit, and each RO represents an olefin unit other than ethylene; and unit formula (B3-4): , where subscripts a, f, g, t, and u, and R1 are as described above. Each R7 is independently a monovalent hydrocarbon group of 1 to 20 carbon atoms. 5. A method for forming product with a siloxane bond, the method comprising: 1) combining starting materials comprising A) a fluorinated triarylborane Lewis acid of formula ; where each of Ro1, Ro2, Ro3, Ro4, Ro5, Ro6, Rm1, Rm2, Rm3, Rm4, Rm5, Rm6, Rp1, Rp2, and Rp3 is independently selected from H, F, or CF3; R includes a functional group or a functional polymer group; and subscript x is 0 or 1; with the provisos that: not all of Ro1, Ro2, Ro3, Ro4, Ro5, Ro6, Rm1, Rm2, Rm3, Rm4, Rm5, Rm6, Rp1, Rp2, and Rp3 can be F simultaneously; not all of Ro1, Ro2, Ro3, Ro4, Ro5, Ro6, Rm1, Rm2, Rm3, Rm4, Rm5, Rm6, Rp1, Rp2, and Rp3 can be H simultaneously; and when two or more of Ro1, Ro2, Ro3, and Ro4 are CF3, then Ro5 and Ro6 are each selected from H or F; B) a silyl hydride having at least one silicon-bonded hydrogen atom per molecule, and C) water; thereby reacting the silicon-bonded hydrogen atom to form the siloxane bond and a by-product comprising hydrogen. 6. The method of claim 5, where starting material A) 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; 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). 7. The method of claim 5 or claim 6, where B) the silyl hydride is selected from the group consisting of: B1) a silane of formula HkSiR5(4-k), where each R5 is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, and subscript k is 1 to 3; B2) a polyorganohydrogensiloxane comprising two or more siloxane units selected from the group consisting of HR42SiO1/2, R43SiO1/2, HR4SiO2/2, R42SiO2/2, R4SiO3/2, HSiO3/2 and SiO4/2, where each R4 is an independently selected monovalent hydrocarbon group, which is free of aliphatic unsaturation; and B3) a polyolefin having a silicon-bonded hydrogen functional group of formula (B3-1): , where each R1 is an independently selected monovalent hydrocarbon group and each subscript a is independently 1 or 2. 8. The method of claim 7, where: starting material B1) is a silane of formula HSiR53, where each R5 is an alkyl group of 1 to 6 carbon atoms; starting material B2) is a polydiorganohydrogensiloxane of unit formula: (HR42SiO1/2)g(R43SiO1/2)h(R42SiO2/2)i(HR4SiO2/2)j, where R4 is as described above, and subscripts g, h, i, and j have values such that g ≥ 0, h ≥ 0, a quantity (g + h) has an average value of 2, i ≥ 0, j ≥ 0, and a quantity (g + j) ≥ 1, and a quantity (i + j) ranges from 0 to 1000; and starting material B3) is an SiH-functional polyolefin copolymer selected from the group consisting of unit formula (B3-2): , where R1 and subscript a are as described above, each R25 is independently H, a monovalent hydrocarbon group of 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms, 1 ≤ M ≤ 10, and 10 ≤ N ≤ 20,000; unit formula (B3-3): Hf[(Ret)t(RO)u]g[ (2 , where subscript a and -f) R1 are as described above, subscript f is 0 to 1, subscripts t and u have relative values such that 0 < t ≤ 1, 0 ≤ u ≤ 1, subscript g is 1 or more, each Ret represents an ethylene unit, and each RO represents an olefin unit, other than ethylene; and unit formula (B3-4): , where subscripts a, f, g, t, and u, and R1 are as described above. Each R7 is independently a monovalent hydrocarbon group of 1 to 20 carbon atoms. 9. The method of any one of claims 5 to 8, where combining in step 1) comprises mixing and heating starting materials A), B), and C) in any order. 10. The method of any one of claims 5 to 9, where starting material A) is dissolved in a solvent before step 1). 11. The method of any one of claims 5 to 10, where starting materials A) and B) are combined before step 1). 12. The method of any one of claims 5 to 11, further comprising: neutralizing residual fluorinated triarylborane Lewis acid in the product. 13. The method of any one of claims 5 to 12, further comprising: during and/or after step 1), removing the by-product comprising H2. |
[0060] To a cold (-78 °C, CO 2 (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 hexanes, 60.0 mmol) with stirring. The reaction mixture was stirred for 1 hour at -78 °C with formation of precipitate. (3,5- Bis(trifluoromethyl)phenyl)diisopropoxyborane (4.82 g, 14.1 mmol) in ether (15 mL) was added slowly. The reaction mixture was stirred for 1 hour at -78 °C (some solids visible), then was allowed to warm to ambient temperature and was stirred overnight to give a clear solution. The volatiles were removed under reduced pressure to give a crystalline-appearing solid. The solid was dissolved in hexane, the solution was filtered and placed in the freezer over the weekend. A large amount of crystalline material formed. The supernatant was decanted and the volatiles were removed under reduced pressure to give a colorless crystalline material. Yield of material: 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. [0061] Preparation of bis(3,5-bis(trifluoromethyl)phenyl)isopropoxy borane was performed as follows: To a solution of lithium(diethyletherate) 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) with immediate formation of precipitate. The reaction mixture was stirred for one hour 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. Synthetic Procedures – Preparation of Catalysts [0062] Catalyst Sample C1, tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct, was prepared as follows: [0063] n-Butyllithium (5.00 mL, 2.5 M in hexanes, 12.7 mmol) was added slowly dropwise to a cold (- 78 °C, CO 2 (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 for 1 hour at -78 °C. Isopropoxy-bis(3,5- bis(trifluoromethyl)phenyl)borane (6.29 g, 12.7 mmol) in ether (10 mL) was added slowly. 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 a minimum of boiling ether and the solution was placed in the freezer. After cooling overnight, the supernatant was decanted from the crystals which had formed and the crystals were dried under reduced pressure to give 6.74 g. A second crop of crystalline material (1.54 g) was obtained from concentrating the supernatant solution and cooling in the freezer overnight. Total yield: 8.28 g, 75.6%. 1 H NMR (400 MHz, Benzene-d 6 ) 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-d 6 ) 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-d 6 ) δ -62.76. 11 B NMR (160 MHz, Benzene-d 6 ) δ 1.56.
[0064] 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 were removed under reduced pressure to give the product as a colorless solid, 4.80 g, 95.2%. [0065] Part 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%. THF adduct: 1 H NMR (400 MHz, Benzene-d 6 ) δ 7.80 – 7.78 (m, 6H), 7.72 (dq, J = 1.8, 0.9 Hz, 3H), 2.90 – 2.83 (m, 4H), 0.57 – 0.49 (m, 4H). 13 C NMR (101 MHz, Benzene-d 6 ) 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-d 6 ) δ -62.95. 11 B NMR (160 MHz, Benzene-d 6 ) δ 11.84. [0066] Catalyst sample C2, bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl) borane THF adduct, was prepared as follows. [0067] n-Butyllithium (4.70 mL, 2.535 M in hexanes, 11.9 mmol) was added slowly dropwise to a cold (-78 °C, CO 2 (s)/acetone bath) solution of 1-bromo-4-trifluoromethylbenzene (2.750 g, 12.22 mmol) in diethyl ether (200 mL). The reaction mixture was stirred for 3 hours at -78 °C. Isopropoxybis(3,5- bis(trifluoromethyl)phenyl)borane (5.910 g, 11.91 mmol) in diethyl ether (15 mL) was added slowly. The reaction mixture was allowed to warm to ambient temperature while 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 stirred at a rapid rate with hexane (100 mL) overnight (some cloudiness develops). The hexane layer was decanted off, 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 hadn’t dissolved was discarded. The volatiles were removed under reduced pressure from the filtrate to give a yellow oil. The oil was dissolved in diethyl ether (100 mL) and trimethylsilylchloride (TMSCl, 1.5 g, 13.8 mmol) was added. Within 30 minutes copious precipitate had formed. The reaction mixture was allowed to stir overnight. The reaction mixture was filtered and the volatiles were removed under reduced pressure to give a pasty beige sludge. NMR spectra showed nearly complete reaction. The product was dissolved in ether and more 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. Several 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 spectra of the borane-THF complex: 1 H NMR (400 MHz, Benzene-d 6 ) δ 7.83 (s, 4H), 7.78 (tq, J = 1.7, 0.8 Hz, 2H), 7.41 (dq, J = 7.4, 0.8 Hz, 2H), 7.07 (dq, J = 7.5, 0.9 Hz, 2H), 3.04 – 2.96 (m, 4H), 0.70 – 0.62 (m, 4H). 13 C NMR (126 MHz, Benzene-d 6 ) 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-d 6 ) δ -62.56 (s, 3F), -62.78 (s, 12F). 11 B NMR (160 MHz, Benzene-d 6 ) δ 18.54. [0068] Catalyst sample C3, bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)bo rane THF adduct, was prepared as follows:
Preparation of lithium bis(diethyletherate) bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)- isopropoxyborate [0069] In a N 2 -purged glove box, 2.06 g (9.78 mmol) of 1-bromo-2,4,6-trifluorobenzene was combined 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 being removed from the glove box. 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 chill. A 2.5 M solution of n-butyllithium in hexane (4.3 mL, 10.8 mmol) was added via syringe to the cold solution. 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 glove box and drawn up into a syringe. The solution was injected into the flask containing the cold aryl lithium solution at -78 °C and the mixture was stirred for half an hour at this temperature. The dry ice/acetone bath was removed and the reaction mixture was allowed to slowly warm to room temperature while stirring overnight. Then next morning, all volatiles were removed under vacuum to yield a sticky yellow solid. The flask was returned to the glove box and the sticky yellow material was extracted with 1) 80 mL of pentane, 2) 80 mL of hexanes, and 3) 60 mL of a 50/50 ether/hexanes mixture. All three solutions were placed in the glove box freezer overnight (-40 °C) and white crystalline material precipitated from 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, approx. 5.5 mmol of desired lithium salt, 56%). It should be noted that pure material was not obtained; the lithium salt was contaminated with the isopropoxyborane starting material (12%-22% contaminated, depending on the batch of solid material collected). It was decided to proceed to the next step in the reaction without any further purification of the isolated material. 1 H NMR (400 MHz, Benzene-d 6 ) δ 8.26 (s, 4H, ortho-ArCH), 7.80 (s, 2H, para-ArCH), 6.22-6.07 (m, 2H, ortho-ArCH), 3.68 (hept, J = 5.8 Hz, 1H, CH(CH 3 ) 2 ), 3.07 (q, J = 7.1 Hz, 8H, OCH 2 ), 0.81 (t, J = 7.1 Hz, 12H, OCH 2 CH 3 ), 0.67 (d, J = 6.2 Hz, 6H, CH(CH 3 ) 2 ). 13 C NMR (101 MHz, Benzene-d 6 ) 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 = 31.9 Hz, ArC-CF 3 ), 125.5 (q, J = 272.4 Hz, CF 3 ), 119.9 (p, J = 4.0 Hz, para-ArCH), 101.0 (ddd, J = 36.6, 24.0, 3.7 Hz, meta-ArCH), 65.9 (s, OCH(CH 3 ) 2 ), 65.8 (s, OCH 2 CH 3 ), 25.7 (s, OCH(CH 3 ) 2 ), 14.7 (s, OCH 2 CH 3 ). 19 F NMR (376 MHz, Benzene-d 6 ) δ -62.7 (s, 12F, CF 3 ), -104.4 (br s, 2F, ortho-ArF), -112.3 (m, 1F, para-ArF). Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoroborane [0070] In a N 2 -purged glove box, 3.30 g (78% pure, 3.29 mmol) of the lithium borate salt was dissolved in 60 mL of diethyl ether to form a colorless solution (note: the lithium borane salt was contaminated with 22% bis(3,5-bis(trifluoromethyl)phenyl)isopropoxyborane). Trimethylsilylchloride (1.0 mL, 7.9 mmol) was added with stirring to the solution at room temperature. There was no immediate sign of a reaction. The mixture was allowed to stir overnight at room temperature. The next morning, a copious amount of LiCl precipitate had formed in the flask. An aliquot of the reaction mixture was removed and analyzed by 19 F NMR spectroscopy to confirm that the reaction had gone to completion. The reaction mixture was filtered through Celite to remove LiCl and the filtrate was pumped down to dryness. The resultant sticky white solid was extracted with 80-90 mL of hexanes and filtered again. The hexanes solution was placed in the glove box 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 hour. Multinuclear NMR spectroscopy confirmed formation of the desired material in pure form. Yield: 0.992 g, 1.75 mmol, 53.2%. 1 H NMR (400 MHz, Benzene-d 6 ) δ 7.88 (s, 6H, ArCH on CF 3 -substituted ring), 6.03 (m, 2H, ArCH on 2,4,6-trifluorophenyl ring). 13 C NMR (101 MHz, Benzene-d 6 ) δ 167.4 (dt, J = 257.6, 16.2 Hz, para- ArCF), 166.2 (dt, J = 253.5, 15.2 Hz, ortho-ArCF), 142.8 (br s, ArC), 137.5 (d, J = 3.0 Hz, ortho-ArCH), 132.1 (q, J = 33.4 Hz, ArC-CF 3 ), 126.9 (pent, J = 4.0 Hz, para-ArCH), 124.1 (q, J = 273.0 Hz, CF 3 ), 112.6 (br s, ArC), 101.6 (ddd, J = 29.0, 24.9, 3.7 Hz, meta-ArCH). 19 F NMR (376 MHz, Benzene-d 6 ) δ - 63.1 (s, 12F, CF 3 ), -92.4 (m, 2F, ortho-ArCF), -98.5 (s, 1F, para-ArCF). 11 B NMR (160 MHz, Benzene-d 6 ) δ 62.9 (broad s). Preparation of THF adduct of bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluoroborane [0071] In a N 2 -purged glove box, 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 jar and dissolved in 50 mL of THF. The THF was removed under vacuum with stirring to yield a white solid. The solid was triturated with 40 mL of 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 %. 1 H NMR (400 MHz, Benzene-d 6 ) δ 7.96 (s, 4H, ortho-ArCH), 7.79 (s, 2H, para-ArCH), 6.16 (t, J = 8.0 Hz, 2H, meta-ArCH), 3.10 (m, 4H, OCH 2 ), 0.79 (m, 4H, CH 2 ). 13 C NMR (101 MHz, Benzene-d 6 ) δ 165.3 (ddd, J = 245.4, 17.7, 14.3 Hz, ortho-ArCF), 163.9 (dd, J = 249.5, 16.2 Hz, para-ArCF), 148.4 (br s, ArC), 134.0 (s, ortho-ArCH), 131.4 (q, J = 32.4 Hz, ArC-CF 3 ), 121.8 (m, para-ArCH), 124.8 (q, J = 272.7 Hz, CF 3 ), 101.3 (ddd, J = 32.8, 24.2, 3.2 Hz, meta-ArCH), 72.6 (s, OCH 2 ), 24.8 (s, CH 2 ). 19 F NMR (376 MHz, Benzene-d 6 ) δ -62.8 (s, 12F, CF 3 ), -96.9 (s, 2F, ortho-ArCF), -108.5 (s, 1F, para- ArCF). 11 B NMR (160 MHz, Benzene-d 6 ) δ 13.2 (broad s). [0072] Catalyst sample C4, bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl) THF adduct, was prepared as follows:
Preparation of lithium bis(diethyletherate) bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)- isopropoxy borate [0073] n-Butyllithium (3.00 mL, 2.48 M in hexanes, 7.44 mmol) was added slowly dropwise to a cold (- 78 °C, CO 2 (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 for 1 hour at -78 °C and then a solution of bis(3,5- bis(trifluoromethyl)phenyl)isopropoxyborane (3.69 g, 7.44 mmol) in ether (10 mL) was added slowly. Precipitate formed while the reaction mixture was allowed to warm to ambient temperature. By the time the reaction mixture had reached room temperature, the precipitate had dissolved to give 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 a minimum of boiling ether and the solution was placed in the glove box freezer (−33 °C). After cooling overnight, the supernatant was decanted from the crystals which had formed. The crystals were dried under reduced pressure. Yield: 6.85 g, 88.4%. 1 H NMR (400 MHz, Benzene-d 6 ) δ 8.31 (s, 4H), 7.77 (tt, J = 2.0, 0.9 Hz, 2H), 6.60 (dq, J = 8.8, 7.5 Hz, 1H), 6.47 – 6.41 (m, 2H), 3.71 (hept, J = 6.2 Hz, 1H), 3.05 (qd, J = 7.1, 0.7 Hz, 8H), 0.82 (td, J = 7.1, 0.6 Hz, 12H), 0.68 (d, J = 6.2 Hz, 6H). 13 C NMR (126 MHz, Benzene-d 6 ) δ 164.45 (dd, J = 249.6, 11.3 Hz), 142.11, 137.21, 136.78 (t, J = 3.8 Hz), 135.51 (t, J = 10.8 Hz), 131.28 (q, J = 33.3 Hz), 126.10 (p, J = 3.8 Hz), 123.30 (q, J = 273.1 Hz), 111.72 – 111.40 (m), 73.82, 65.57, 15.11, 2.57. 19 F NMR (376 MHz, Benzene-d 6 ) δ -62.64, -106.66. 11 B NMR (160 MHz, Benzene-d 6 ) δ 0.68 (s). Preparation of THF adduct of bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)boran e [0074] Lithium bis(diethyletherate) 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. Precipitate began to form within 15 minutes. The reaction mixture was allowed to stir over the weekend. By Monday, the volatiles had evaporated away (non-sealed 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. NMR spectra showed clean borane, but with only about 86% of the required ether for a mono etherate complex. The product was dissolved in ether to give a hazy solution. THF (6 mL) was added and the solution became crystal clear. 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%. 1 H NMR (400 MHz, Benzene-d 6 ) δ 8.02 (d, J = 1.8 Hz, 2H), 7.77 (dq, J = 1.9, 0.9 Hz, 1H), 6.71 – 6.60 (m, 0H), 6.48 (t, J = 8.4 Hz, 1H), 3.17 – 3.09 (m, 2H), 0.77 – 0.68 (m, 2H). 13 C NMR (101 MHz, Benzene-d 6 ) 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-d 6 ) δ -62.80, -99.69 (t, J = 7.5 Hz). 11 B NMR (160 MHz, Benzene-d 6 ) δ 12.2 (s). [0075] Catalyst Sample C5, bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl) phenyl)borane, was prepared as follows: Preparation of lithium isopropoxy bis(3,5-bis(trifluoromethyl)phenyl)(2,5- bis(trifluoromethyl)phenyl)borate [0076] n-Butyllithium (4.00 mL, 2.535 M in hexanes, 10.14 mmol) was added slowly to a cold (-78 °C, CO 2 (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 for 1 hour at -78 °C. Isopropoxy-bis(3,5- bis(trifluoromethyl)phenyl)borane (5.036 g, 10.15 mmol) in ether (18 mL) was added slowly. The reaction mixture was stirred for several hours at -78 °C. The solution was warmed to ambient temperature while stirring overnight to give a pale-yellow clear solution. The volatiles were removed from the reaction mixture to give a yellow oil. The oil was extracted with benzene. There was nothing insoluble. The volatiles were removed from the reaction mixture to give a yellow oil. The yield was 7.88 g, 98.3%. 1 H NMR (400 MHz, Benzene-d 6 ) δ 8.06 (s, 1H), 8.00 (s, 4H), 7.70 (dt, J = 1.8, 0.9 Hz, 2H), 7.40 (d, J = 8.3 Hz, 1H), 7.19 (d, J = 8.4 Hz, 1H), 3.79 (hept, J = 6.1 Hz, 1H), 2.78 (q, J = 7.1 Hz, 4H), 0.73 (d, J = 6.1 Hz, 6H), 0.54 (t, J = 7.1 Hz, 6H). 13 C NMR (101 MHz, Benzene-d 6 ) δ 158.31, 153.97, 135.44 (q, J = 3.7 Hz), 135.23, 133.55 (t, J = 4.1 Hz), 133.25, 133.18, 132.37 (d, J = 97.8 Hz), 130.92 (q, J = 32.0 Hz), 127.80 (q, J = 273.9 Hz), 124.92 (q, J = 272.5 Hz), 124.66 (q, J = 272.8 Hz), 123.86 (q, J = 3.8 Hz), 119.86 (p, J = 3.9 Hz), 66.24, 66.17, 25.60, 13.94. 19 F NMR (376 MHz, Benzene-d 6 ) δ -55.30 – -55.51 (m), -62.82, -63.61. 11 B NMR (160 MHz, Benzene-d 6 ) δ 2.16. Preparation of bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl) phenyl)borane [0077] Lithium(diethyletherate) 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 allowed to stir overnight to give a yellow solution with 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 the 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 compound: 1 H NMR (400 MHz, Benzene-d 6 ) δ 7.87 (s, 2H), 7.85 (s, 4H), 7.29 (s, 1H), 7.11 (d, J = 1.2 Hz, 2H). 13 C NMR (126 MHz, Benzene-d 6 ) δ 140.87, 140.75, 137.49 (d, J = 3.8 Hz), 135.11 (q, J = 31.7 Hz), 133.26 (q, J = 33.0 Hz), 132.03 (q, J = 33.6 Hz), 128.29, 127.34 (q, J = 3.8 Hz), 127.11 (q, J = 4.0 Hz), 127.01 (q, J = 4.0 Hz), 124.46 (q, J = 274.3 Hz), 123.70 (q, J = 273.2 Hz), 123.49 (q, J = 272.9 Hz). 19 F NMR (376 MHz, Benzene-d 6 ) δ -56.98, -63.43, -63.47. 11 B NMR (160 MHz, Benzene- d 6 ) δ 64.37. [0078] Catalyst Sample C6, (3,5-bis(trifluoromethyl)phenyl)bis(2,5- bis(trifluoromethyl)phenyl)borane, was prepared as follows: Preparation of lithium diisopropoxy (3,5-bis(trifluoromethyl)phenyl)(2,5- bis(trifluoromethyl)phenyl)borate [0079] To a cold (between -101 °C and -99 °C, CO 2 (s), then N 2 (l) 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- butyllithium (4.00 mL, 2.535 M in hexanes, 10.14 mmol) with stirring. The reaction mixture was stirred for 2 hours at around -100 °C then was allowed to warm up to -78 °C. Bis(isopropoxy)(3,5- bis(trifluoromethyl)phenyl)borane (3.510 g, 10.26 mmol) in ether (10 mL) was added slowly. The reaction mixture was allowed to warm to ambient temperature while stirring overnight. The volatiles were removed from the pale-yellow nearly clear solution under reduced pressure to give a crystalline-appearing solid. The solid was dissolved in ether (10 mL) and placed in the freezer. Nothing precipitated. The ether was evaporated and the yellow solid was dissolved in hexane, filtered, and concentrated under a nitrogen stream to give 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. Crystalline matter formed. The supernatant was pipetted out and discarded. The crystalline residue was dried under reduced pressure: 2.017 g. Total yield: 5.335 g, 82.79%. 1 H NMR (400 MHz, Benzene-d 6 ) δ 8.39 (s, 2H), 8.26 (s, 1H), 7.90 (dq, J = 1.8, 0.9 Hz, 1H), 7.56 (d, J = 8.2 Hz, 1H), 7.27 (ddt, J = 7.9, 1.7, 0.8 Hz, 1H), 3.18 (hept, J = 6.0 Hz, 2H), 2.92 (q, J = 7.1 Hz, 4H), 0.89 (t, J = 7.1 Hz, 6H), 0.78 (d, J = 6.1 Hz, 6H), 0.68 (d, J = 6.0 Hz, 6H). 13 C NMR (101 MHz, Benzene-d 6 ) δ 153.10, 136.65 (q, J = 29.6 Hz), 134.81 (dd, J = 2.7Hz, 1.9 Hz), 133.93 (q, J = 3.6 Hz), 131.93 (q, J = 31.6 Hz), 131.35, 129.76 (q, J = 31.9 Hz), 127.26 (q, J = 274.6 Hz), 125.17 (d, J = 272.4 Hz), 124.89 (q, J = 272.8 Hz), 123.25 (q, J = 3.9 Hz), 119.89 (p, J = 3.9 Hz), 66.42, 64.08, 25.49, 24.57, 14.36. 19 F NMR (376 MHz, Benzene-d 6 ) δ -55.79, -62.66, -63.30. 11 B NMR (160 MHz, Benzene-d 6 ) δ 5.32.
[0080] To a solution of lithium(diethyletherate) 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) with rapid formation of precipitate. The reaction mixture was allowed to stir overnight. The reaction mixture was filtered and the volatiles were removed under reduced pressure. NMR analysis showed the reaction was complete. Some putative TMS-O-iPr ether was present, too. The second crop of lithium diisopropoxy (3,5- bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)b orate prepared as described above was treated similarly (2.017 g, 3.17 mmol, of lithium salt; 2.0 mL of TMSCl) and stirred for 3 hours. The 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. The volatiles were removed under reduced pressure. The residue was extracted with hexane, filtered, and the volatiles were removed overnight at 40 °C under reduced pressure to give the product as a yellow oil, 3.4703 g, 83.42%. 1 H NMR (400 MHz, Benzene-d 6 ) δ 8.05 (d, J = 1.8 Hz, 2H), 7.80 (d, J = 2.3 Hz, 1H), 7.34 (d, J = 1.9 Hz, 1H), 7.12 (d, J = 6.5 Hz, 1H), 7.10 (d, J = 6.7 Hz, 1H), 3.78 (hept, J = 6.1 Hz, 1H), 0.85 (d, J = 6.1 Hz, 6H). 13 C NMR (101 MHz, Benzene- d 6 ) δ 139.07, 136.28, 135.37 (q, J = 31.8 Hz), 134.93 (d, J = 3.9 Hz), 133.49 (q, J = 32.7 Hz), 131.50 (q, J = 33.0 Hz), 127.87, 126.95 (dq, J = 7.5, 3.7 Hz), 126.46 (q, J = 3.7 Hz), 125.41 (hex, J = 3.8 Hz), 124.57 (q, J = 273.9 Hz), 123.98 (q, J = 272.8 Hz), 123.90 (q, J = 273.0 Hz), 72.49, 23.71. 19 F NMR (376 MHz, Benzene-d 6 ) δ -60.31, -63.27 (d, J = 3.3 Hz), -63.47 (d, J = 3.3 Hz). 11 B NMR (160 MHz, Benzene-d 6 ) δ 41.28.
Preparation of lithium isopropoxy bis(2,5-bis(trifluoromethyl)phenyl)(3,5- bis(trifluoromethyl)phenyl)borate [0081] n-Butyllithium (2.40 mL, 2.535 M in hexanes, 6.08 mmol) was added slowly to a cold (-78 °C, CO 2 (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 for 1 hour at -78 °C. Isopropoxy(2,5-bis(trifluoromethyl)phenyl)(3,5- bis(trifluoromethyl)phenyl)borane (3.022 g, 6.09 mmol) in ether (18 mL) was added slowly. The reaction mixture was stirred for several hours at -78 °C. The solution was allowed to warm to ambient temperature while stirring overnight to give a pale-yellow clear solution. The volatiles were removed from the reaction mixture to give a yellow oil. The oil was extracted with benzene. There was nothing insoluble. The volatiles were removed from the reaction mixture to give a yellow oil. The yield was 4.21 g, 87.6%. 1 H NMR (400 MHz, Benzene-d 6 ) δ 8.30 (s, 2H), 8.12 (s, 2H), 7.65 (dt, J = 1.7, 0.9 Hz, 1H), 7.27 (d, J = 8.2 Hz, 2H), 7.08 (d, J = 8.2 Hz, 2H), 3.87 (hept, J = 6.2 Hz, 1H), 2.91 (q, J = 7.1 Hz, 4H), 0.65 (d, J = 6.2 Hz, 6H), 0.63 (t, J = 7.1 Hz, 6H). 13 C NMR (101 MHz, Benzene-d 6 ) 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-d 6 ) δ -56.31, - 62.89, -63.76. 11 B NMR (160 MHz, Benzene-d 6 ) δ 2.98. [0082] To a solution of lithium(diethyletherate) isopropoxy-bis(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. Within 15 minutes, precipitate formed in 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 pale solid, 3.109 g, 96.53%. 1 H NMR (500 MHz, Benzene-d 6 ) δ 7.90 (s, 1H), 7.83 (s, 1H), 7.66 (s, 3H), 7.09 (s, 5H), 7.09 (s, 5H). 13 C NMR (126 MHz, Benzene- d 6 ) 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-d 6 ) δ -56.40, -63.31, -63.58. 11 B NMR (160 MHz, Benzene-d 6 ) δ 67.58. [0083] Catalyst Sample C7 was prepared as follows: Preparation of tris(2,5-bis(trifluoromethyl)phenyl)borane [0084] This reaction was carried out in a manner similar to a previously reported procedure. 2 Isopropylmagnesium 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) which was 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 boron trifluoride diethyletherate (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 while it was stirred over the weekend. The volatiles were removed from the solution to give a reddish solid, 12.77 g. The residue was extracted with toluene and filtered. The volatiles were removed under reduced pressure to give a pink powder, 10.75 g. The solids were extracted with methylene chloride to give a light violet solution. The solution was placed overnight in the freezer. The supernatant was decanted from the very light pinkish crystalline material which formed. The material was dried overnight under reduced pressure. Yield: 7.0003 g, 55.73%. TH-free product: 1 H NMR (400 MHz, Benzene-d 6 ) 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-d 6 ) δ 141.10, 136.50 (q, J = 32.2 Hz), 132.81 (q, J = 33.1 Hz), 2 Herrington, T. J.; Thom, A. J. W.; White, A. J. P.; Ashley, A. E. Dalton Trans.2012, 41, 9019. 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-d 6 ) δ -56.48, -63.77. 11 B NMR (160 MHz, Benzene-d 6 ) δ 68.81. [0085] Catalyst sample C8, bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4- trifluoromethylphenyl)borane THF adduct, was prepared as follows: Preparation of lithium(tetrahydrofuranate) bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4- trifluoromethylphenyl)isopropoxyborate n-Butyllithium (3.00 mL, 2.54 M in hexanes, 7.61 mmol) was added to a cold (between -101 °C and -99 °C, CO 2 (s), then N 2 (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) with stirring. The reaction mixture was stirred for 2 hours at -100 °C then was allowed to warm up to -76 °C. Bis(3,5-bis(trifluoromethyl)phenyl)isopropoxy-borane (3.78 g, 7.61 mmol) in ether (10 mL) was added slowly to the reaction mixture. The reaction mixture was allowed to warm slowly to ambient temperature while 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. It had limited solubility in benzene. The aliquot was dissolved in THF and the volatiles were removed under reduced pressure and then analyzed again by NMR in benzene. Yield: 6.16 g, 93.2%. 1H NMR (500 MHz, Benzene-d 6 ) δ 8.32 (s, 4H), 7.85 (s, 2H), 3.47 (h, J = 6.2 Hz, 1H), 3.26 – 3.17 (m, 4H), 1.24 – 1.16 (m, 4H), 0.55 (d, J = 6.2 Hz, 6H). 13 C NMR (126 MHz, Benzene-d 6 ) δ 144.07 (d, J = 259.4 Hz), 134.41, 133.82, 133.48 (d, J = 187.5 Hz), 130.59 (q, J = 32.2 Hz), 130.45 (q, J = 31.8 Hz), 126.40 – 123.43 (m), 125.84, 124.97 (q, J = 272.4 Hz), 119.94 (p, J = 4.0 Hz), 118.92 (d, J = 190.9 Hz), 109.57 (d, J = 22.7 Hz), 68.38, 65.30, 25.64, 25.13. 19 F NMR (470 MHz, Benzene-d 6 ) δ -56.26 (t, J = 20.7 Hz), -62.59, -137.04, -141.73. 11 B NMR (160 MHz, Benzene-d 6 ) δ 1.20.
[0086] 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, analysis of an aliquot of the reaction mixture by 19 F NMR spectroscopy revealed that no reaction had occurred. Hydrogen chloride solution in ether (7.00 mL, 2.0 M, 14.0 mmol) was added and the reaction mixture was stirred overnight. The next day, analysis of an aliquot of the reaction mixture by 19 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 resultant 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 remained in the coordination sphere of the borane. Yield of the borane as a isopropanol adduct: 2.45 g, 52.8%. [0087] 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 allowed to evaporate slowly to give 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 had not displaced the coordinated alcohol. The supernatant solution from the crystals and the hexane washings were combined and concentrated under vacuum to give 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 showed the presence of coordinated isopropanol, but little or no THF. THF was added and then the volatiles were removed under reduced pressure. NMR analysis showed the presence of THF, but still some isopropanol. The solid was dissolved in THF and then pumped off. 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-d 6 ) δ 7.87 (s, 4H), 7.80 (s, 4H), 3.02 – 2.93 (m, 4H), 0.78 – 0.72 (m, 4H). 13 C NMR (126 MHz, Benzene-d 6 ) δ 147.98 (td, J = 16.5, 3.6 Hz), 146.05 (tt, J = 11.8, 4.1 Hz), 145.58 (d, J = 20.9 Hz), 143.50 (d, J = 20.1 Hz), 133.44, 131.39 (q, J = 32.6 Hz), 124.24 (q, J = 272.7 Hz), 121.78 (t, J = 4.0 Hz), 121.45 (q, J = 274.4 Hz), 109.38 – 108.10 (m), 73.75, 23.90. 19 F NMR (376 MHz, Benzene-d 6 ) 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-d 6 ) δ 7.22. The catalyst samples prepared as described above in Reference Example 2 are shown below. [0088] Structures of fluorinated arylborane Lewis acid catalyst samples C1 to C8, and commercially available FAB, are shown above. Structure C1 is tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct (corresponding to starting material A1) in the claims). Structure C2 is bis(3,5- bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct corresponding to starting material A2) in the claims). Structure C3 is bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6- trifluorophenyl)borane THF adduct (corresponding to starting material A3) in the claims). Structure C4 is bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)boran e THF adduct (corresponding to starting material A4) in the claims). Structure C5 is bis(3,5-bis(trifluoromethyl)phenyl)(2,5- bis(trifluoromethyl)phenyl)borane (corresponding to starting material A5) in the claims). Structure C6 is (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl) phenyl)borane (corresponding to starting material A6) in the claims). Structure C7, which is comparative, 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 starting material A7) in the claims). Reference Example 3 – Screening Study [0089] Fluorinated triarylborane Lewis acids prepared as described above were evaluated for SiH coupling in the presence of water as follows. In a nitrogen-purged glovebox, solutions of the fluorinated triarylborane Lewis acid samples shown above were prepared in 10-mL glass vials (ex. FAB, 30.7 mg was dissolved in 5 mL of toluene). The silane (ex: TES, 38.4 µL, 2 equiv.), an internal standard (IS, mesitylene, 16.8 µL, 1 equiv.) were placed in an NMR tube. The catalyst (0.5 mL, 5 mol%) was delivered as a toluene stock solution via pipet. The tube was capped and 1 H NMR spectra were taken at regular time intervals. Conversion was established in comparison to the internal standard (Si-H bond to IS or Product to IS when possible) after 2h and 24h. SiH coupling reaction in the presence of water. Table 2 SiH coupling reaction in the presence of water [0090] Without wishing to be bound by theory, it is thought that C7 was too sterically bulky to catalyze the SiH coupling reaction under the conditions tested, and that this demonstrates that not all fluorinated aryl boranes will catalyze the reaction. Reference Example 4 - General Procedure for Preparation of SiH-Containing Polyolefin Copolymers (copolymer of ethylene, octene, and 5-hexenyldimethylsilane (HDMS) or 7-octenyldimethylsilane (ODMS)) [0091] Batch reactor polymerizations were conducted in a 2-L Parr batch reactor. The reactor was heated by an electrical heating mantle and was cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating/cooling system were controlled and monitored by a CAMILE TG process computer. The bottom of the reactor was fitted with a dump valve, which empties the reactor contents into a stainless steel dump pot. The dump pot was vented to a 30-gal. blow-down tank, with both the pot and the tank purged with nitrogen. Before use, all solvents used for polymerization or catalyst makeup were run through solvent purification columns to remove any impurities that may affect polymerization. The 1-octene and ISOPAR-E were passed through two columns, the first containing A2 alumina, the second containing Q5 reactant. (ISOPAR-E is an isoparaffin fluid, typically containing less than 1 ppm benzene and less than 1 ppm sulfur, which is commercially available from ExxonMobil Chemical Company.) The ethylene was passed through 2 columns, the first containing A204 alumina and 4Ǻ mol sieves, the second containing Q5 reactant. The N 2 , used for transfers, was passed through a single column containing A204 alumna, 4Ǻ mol sieves and Q5 reactant. [0092] The desired amount of 5-hexenyldimethylsilane monomer or 7-octenyldimethylsilane monomer was added via shot tank to the load column, followed by ISOPAR-E solvent and/or 1-octene, depending on desired reactor load. The load column was filled to the load set points by use of a lab scale to which the load column is mounted. After liquid feed addition, the reactor was heated up to the polymerization temperature set point. If ethylene was used, it was added to the reactor when the reactor was at reaction temperature to maintain the reaction pressure set point. Ethylene addition amounts were monitored by a micro-motion flow meter. [0093] The scavenger, MMAO-3A, was handled in an inert atmosphere glove box, drawn into a syringe and pressure-transferred into the catalyst shot tank. This was followed by 3 rinses of toluene, 5 mL each, before being injected into the reactor. The procatalyst and activators were mixed with the appropriate amount of purified toluene to achieve a desired molarity solution. The catalyst and activators were handled in an inert atmosphere glove box, drawn into a syringe and pressure-transferred into the catalyst shot tank. This was followed by 3 rinses of toluene, 5 mL each. Immediately after catalyst addition the run timer begins. If ethylene was used, it was then added by the CAMILE to maintain the reaction pressure set point in the reactor. These polymerizations were run for 10 min., then the agitator was stopped and the bottom dump valve was opened to empty reactor contents into the dump pot. The dump pot contents were poured into trays placed in a lab hood where the solvent was evaporated off overnight. The trays containing the remaining polymer were then transferred to a vacuum oven, where they were heated up to 140 °C under vacuum to remove any remaining solvent. After the trays cooled to ambient temperature, the polymers were weighed for yield/efficiencies and submitted for polymer testing. [0094] Copolymer samples were prepared following the batch reactor process using the following conditions: for the first copolymer in Table 3, 120 °C, 12 g of ethylene loaded, 3.5 mL of 5- hexenyldimethylsilane, 52 g of 1-octene, 588 g of ISOPAR E, 20 µmol of MMAO-3A, 1.2 eq. of bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate to 1.0 eq. of procatalyst; for the second copolymer in Table 3, 120 °C, 12 g of ethylene loaded, 4 mL of 7- octenyldimethylsilane, 58 g of 1-octene, 596 g of ISOPAR-E, 20 µmol of MMAO-3A, 1.2 eq. of bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate to 1.0 eq. of procatalyst; and for the third copolymer in Table 3, 120 °C, 12 g of ethylene loaded, 4 mL of 7- octenyldimethylsilane, 58 g of 1-octene, 592 g of ISOPAR-E, 20 µmol of MMAO-3A, 1.2 eq. of bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate to 1.0 eq. of procatalyst. The amount of procatalyst used was adjusted to reach a desired efficiency. The reactor pressure and temperature were kept constant by feeding ethylene during the polymerization and cooling the reactor as needed. The polymerization was run to 23 g of ethylene uptake. All polymerizations were performed with bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate as the activator and MMAO as the scavenger. Properties for the silicone-polyolefin copolymers (elastomers) are shown in Table 3. Table 3 Silicone-polyolefin copolymer (elastomer) information Reference Example 5 – Crosslinking study with SiH functional polyolefin copolymer [0095] Samples of fluorinated triarylborane Lewis acids C4, C5, C6, and C7 prepared as described above were selected to determine their feasibility to catalyze reaction of the silicon-bonded hydrogen atoms in a copolymer of ethylene, 1-octene, and either HDMS or ODMS prepared as described in Reference Example 4. Tris(pentafluorophenyl)borane (FAB), which was commercially available, was used as a control. [0096] Solutions of these fluorinated triarylborane Lewis acids (boranes) were made by first weighing solid boranes in a glovebox under a nitrogen atmosphere. The boranes were then removed from the glovebox and mixed with known masses of toluene to make solutions that could be blended into molten copolymers. Care was taken to limit exposure time to air prior to solution creation, and toluene dried over molecular sieves was used as a solvent. All testing of catalyst-laden elastomer samples was initiated within 48 hours of removing catalyst samples from nitrogen atmosphere to limit air or moisture contamination. Solutions of C4, C5, C6, and C7 were added to a melt-blending process such that the loading of each borane was 100 ppm. Melt blending was conducted using a Haake blender with a 20-g bowl, with the temperature set to 80 °C, using a blending rate of 60 rpm.10 g of an elastomer described in Table 3 was blended for 3 minutes until adequately melted, after which 100 µL of borane solution was added. The system was allowed to blend for another 3 minutes until well homogenized, after which the resulting catalyst-laden elastomer was removed and allowed to cool. There was no visual evidence of premature crosslinking of the elastomer during melt blending with C4, C5, C6, and C7 solutions. Premature crosslinking was visually observed when using FAB solutions in the same process. [0097] The resulting catalyst-laden elastomer was then compression-molded into torsion bars (2 mm thick) by compression molding at 90 °C for 4 minutes at 20,000 lbs force. These torsion bars were then moisture-cured by exposure to a humid environment controlled to 85 °C, 85% relative humidity or 25 °C, 85% relative humidity. Bars were removed from the humid environment after either 1 day or 5 days to give some idea of the kinetics of the moisture-cure reaction. After a bar was removed from the humid environment for testing, it was discarded and not used for further testing. Reference Example 6 – Analysis of Samples [0098] Torsion bars were tested via dynamic mechanical analysis (DMA) using an ARES rheometer. Samples were fixed into the instrument and were exposed to a temperature sweep from 25 °C to 250 °C, temperature ramp of 2 °C/min, 1% strain. Moisture-cured crosslinking was monitored by evidence of a temperature-insensitive storage modulus plateau. [0099] The DMA shear storage modulus of the sample containing the C4 borane with 1 day of moisture exposure at 85 °C decreased monotonically with temperature, dropping to approximately 10 2 Pa at 250 °C, indicating minimal crosslinking had occurred during exposure. The DMA shear storage modulus of the sample after 5 days of moisture exposure decreased with temperature until the sample reached approximately 160 °C. The sample then showed a shear storage modulus plateau of approximately 10 4 Pa, indicating a crosslinked network had formed, preventing further melting of the sample with increasing temperature. This test demonstrated the efficacy of the C4 borane for use as a latent condensation catalyst in a polymer system. [0100] The DMA shear storage modulus of the sample containing the C5 borane with 1 day of moisture exposure at 85 °C decreased monotonically with temperature, dropping to approximately 10 4 Pa at 250 °C, indicating minimal crosslinking had occurred during exposure. The DMA shear storage modulus of the sample after 5 days of moisture exposure decreased with temperature until the sample reached 170 °C. [0101] The sample then showed a shear storage modulus plateau of approximately 10 4 Pa, indicating some crosslinking had occurred, preventing further melting of the sample with increasing temperature. This test demonstrated the efficacy of the C5 borane for use as a latent condensation catalyst in a polymer system. [0102] The DMA shear storage modulus of the sample containing the C6 borane with 1 day of moisture exposure at 85 °C decreased monotonically with temperature, dropping to approximately 10 3 Pa at 250 °C, indicating minimal crosslinking had occurred during exposure. The DMA shear storage modulus of the sample after 5 days of moisture exposure decreased with temperature until the sample reached approximately 160 °C. The sample then showed a shear storage modulus plateau of approximately 10 4 Pa, indicating a crosslinked network had formed, preventing further melting of the sample with increasing temperature. This test demonstrated the efficacy of the C6 borane for use as a latent condensation catalyst in a polymer system. [0103] The DMA shear storage modulus of the sample containing the C5 borane with 1 day and 5 days of moisture exposure at 25 °C decreased monotonically with temperature, and the extent of the decrease was the same as that for the sample without any moisture treatment, indicating minimal crosslinking had occurred during moisture exposure at 25 °C. By comparison with the test of C5-containing samples with moisture exposure at 85 °C, this test demonstrated that heating is necessary for C5 as a latent condensation catalyst to effectively cure a polymer system. [0104] The DMA shear storage modulus of the sample containing the C7 with 1 day and 5 days of moisture exposure at both 25 °C and 85 °C decreased monotonically with temperature, and the extent of the decrease was the same as that for the sample without any moisture treatment, indicating minimal crosslinking had occurred during moisture exposure at 25 °C and 85 °C. The two tests demonstrated that C7 did not act sufficiently as a catalyst both below and above the melting point of the polymer system under the conditions tested. [0105] Torsion bars were analyzed using ATR FT-IR spectroscopy at the time points of interest to monitor formation of Si-O-Si bonds and loss of Si-H bonds. Characteristic vibrational frequencies that were monitored for this study are summarized in Table 4. Table 4. Characteristic vibrational frequencies of Si-H and Si-O-Si groups [0106] Spectra for the boranes analyzed (C4 and C5) showed a gradual increase in the siloxane peak region (1000-1130 cm -1 ) as a function of time. The two peaks associated with Si-H vibrations (890 cm -1 and 2080-2280 cm -1 ) also diminished at longer times, which indicated loss of Si-H bonds. The combination of these observations led to the conclusion that at least some of the Si-H groups reacted to give siloxane bonds (Si-O-Si linkages). Additional side reactions may have occurred, evidenced by the emergence of unexpected peaks in both cases at about 1710 cm -1 . It was also observed that there was still substantial unreacted Si-H content in the system, which could either continue to react over longer periods of time, or be too immobile in the partially crosslinked matrix to have the mobility to complete the crosslinking reaction with other unreacted Si-H groups. Additional loadings of these boranes were not tested, however it is hypothesized that higher loadings would lead to more complete utilization of the Si- H content of the copolymer and a greater corresponding crosslink density. [0107] These boranes present a practical controllable route to enable moisture cure of Si-H containing copolymers. FTIR spectra revealed little change of the SiH peak in the C7 sample over time, which was agreement with the model system study where C7 did not catalyze any conversion of SiH under the conditions tested. Industrial Applicability [0108] As demonstrated in the examples shown above, when starting material B) comprises a silyl hydride functional polyolefin, starting materials A) and B) can be combined, e.g., mixed, and do not cure unless and until they are exposed to water. That a silyl hydride (SiH functional material) and catalyst can be combined and stored before use/cure is an unexpected benefit of the composition and method described herein. Problem to be Solved [0109] 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, which have certain drawbacks, described above. An emerging alternative to Pt-based catalysts is the use of tris(pentafluorophenyl)borane (B(C 6 F 5 ) 3 ), referred to herein as FAB. FAB is relatively low-cost, does not contain heavy metals, and has low levels required for catalysis. The use of FAB as a catalyst has been reported in reactions between the Si-H functionality and another functionality useful in curable siloxane compositions or as intermediates. These functionalities include alkoxysilyl functionalities (≡Si-OR) and silanols (≡Si-OH). [0110] In the case of FAB-catalyzed coupling reactions between ≡Si-H and ≡Si-OR, or between ≡Si-H and ≡Si-OH, one major limitation for commercial applications is that the reaction is highly exothermic and occurs very rapidly at room temperature. In the context of large-scale manufacturing of siloxanes, this is problematic because of 1) rapid generation of flammable gas and 2) rapid heating of the reaction mixture. Those factors combined make commercial-scale practice difficult to control, and make proper reaction feed/mixing and monitoring difficult, which can lead to poor reproducibility. [0111] There is an industry need for alternative catalysts, which can promote a reaction between two Si-H moieties in the presence of water in a more controlled manner than FAB. It would be especially desirable to have the ability to control that rate based on the choice of catalysts. Solution [0112] The composition and method described herein employ fluorinated triarylborane Lewis acids as catalysts. These fluorinated triarylborane Lewis acids provide better reaction rate control than FAB. Definitions and Usage of Terms [0113] Abbreviations used in the specification have the definitions in Table 5, below. Table 5 – Abbreviations [0114] 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 hereby incorporated by reference. The articles ‘a’, ‘an’, and ‘the’ each refer to one or more, unless otherwise indicated by the context of specification. The singular includes the plural unless otherwise indicated. The disclosure of ranges includes the range itself and also anything subsumed therein, as well as endpoints. For example, disclosure of a range of 2.0 to 4.0 includes not only the range of 2.0 to 4.0, but also 2.1, 2.3, 3.4, 3.5, and 4.0 individually, as well as any other number subsumed in the range. Furthermore, disclosure of a range of, for example, 2.0 to 4.0 includes the subsets of, 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 in the range. Similarly, the disclosure of Markush groups includes the entire group and also any individual members and subgroups subsumed therein. For example, disclosure of the Markush group a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, includes the member alkyl individually; the subgroup alkyl and aryl; and any other individual member and subgroup subsumed therein. [0115] The term “comprising” and derivatives thereof, such as “comprise” and “comprises” are used herein in their broadest sense to mean and encompass the notions of “including,” “include,” “consist(ing) essentially of,” and “consist(ing) of. The use of “for example,” “e.g.,” “such as,” and “including” to list illustrative examples does not limit to only 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. [0116] Generally, as used herein a hyphen “-” or dash “–” in a range of values is “to” or “through”; a “>” is “above” or “greater-than”; a “≥” is “at least” or “greater-than or equal to”; a “<” is “below” or “less- than”; and a “≤” is “at most” or “less-than or equal to.” On an individual basis, each of the aforementioned applications for patent, patents, and/or patent application publications, is expressly incorporated herein by reference in its entirety in one or more non-limiting embodiments. [0117] It is to be understood that the appended claims are not limited to express and particular compounds, compositions, or methods described in the detailed description, which may vary between particular embodiments which fall within the scope of the appended claims.