ࡱ> 685M bjbj== 2WW<sl  ||||$ 6888888$ v\i\d d d d 6d 6d d  ,pUC|x $0 W XWd Supporting Information General: B(C6F5)3 was purchased from Boulder Scientific and was dried with Cl2SiMe2 followed by sublimation and stored in a glove box. PhMe2SiH was purchased from Aldrich and used without further purification. Imines were either purchased from Aldrich and used as is or were prepared by standard methods. Aldimines were generally prepared by condensing aldehyde and amine in CH2Cl2 followed by purification by recrystallization or distillation and ketimines were prepared by mixing ketone and amine in toluene and heating to reflux (4-24 hours) using Dean-Stark apparatus in the presence of catalytic ZnCl2 and then purified by recrystallization or distillation. Toluene was purified using the Grubbs method, benzene-d6 was distilled from Na/benzophenone ketyl. Hydrosilation reactions were carried out under an argon atmosphere. 1H, 13C and 29Si NMR spectra were referenced relative to TMS at 0 ppm. 11B NMR spectra were referenced relative to BF3(Et2O at 0 ppm. 19F NMR spectra were referenced externally to C6F6 at 163 ppm relative to CFCl3 at 0 ppm. Representative procedure (entry 3, Table 1) for hydrosilation of imines: To an oven-dried round-bottom flask containing N-benzylidine aniline (181 mg, 1.0 mmol) in 1 mL of dry PhCH3 under an Ar atmosphere was added B(C6F5)3 (26 mg, 5 mol%). To this solution was then added PhMe2SiH (160 C Ar.t., 23 hK3&E&MFD BPhsb@[bEmL, 1.05 mmol) via syringe. The reaction mixture was stirred at room temperature for 60 minutes. Upon completion (as determined by GC-MS), the reaction mixture was immediately columned using a hexanes: 10% ethyl acetate/hexanes gradient as the eluent. The product, N-phenylbenzylamine was isolated in 95% yield (174 mg, 0.95 mmol). Its 1H NMR closely matched literature reports (see below for references to spectral data for secondary amines). Preparation of Ion-pair 1: Ph2C=NBn (54 mg, 0.20 mmol) and B(C6F5)3 (102 mg, 0.20 mmol) were dissolved in C6D6 (approximately 0.5 mL) in an NMR tube packed under argon and sealed with rubber septum. PhMe2SiH (32 [95%fKbDbKs^ \95%mL, 0.20 mmol) was then added via syringe leading instantly to a colorless two-layer reaction mixture. 1H, 13C, 19F, 11B and 29Si NMR spectra of the bottom layer were recorded. 1H NMR (400 MHz): d 7.21-7.01 (m, 10H), 6.92-6.84 (m, 4H), 6.81 (d, 2H), 6.70 (d, 2H), 6.64 (m, 2H), 5.20-4.20 (br. S, 1H, B-H), 4.63 (s, 2H, CH2Ph), 0.00 (s, 6H, SiCH3); 13C NMR (100 MHz): d 197.6 (C=N), 137.8, 136.7, 136.1, 135.1, 133.8, 133.6, 132.3, 131.8, 131.6, 131.5, 130.2, 130.1, 129.9, 129.8, 129.4, 129.1, 61.8 (CH2Ph), -0.2 (SiCH3); 19F NMR (282 MHz): d -132.4 ppm (m, 6 F, ortho F s), -163.8 ppm (m, 3 F, para F s), -166.6 ppm (m, 6 F, meta F s); 11B NMR ((6.3 MHz): d -24 ppm; 29Si NMR (79.5 MHz): d 26.9 ppm. Observation of a cross-peak in a 1H-11B HETCOR experiment confirmed the direct H-B bonding relationship. NMR analysis of B(C6F5)3 catalyzed hydrosilation (PhMe2SiH) of Ph2C=NBn: To an NMR tube containing Ph2C=NBn (27 mg, 0.10 mmol) and B(C6F5)3 (5 mg, 0.010 mmol) dissolved in C6D6 was added PhMe2SiH (16 mL, 0.10 mmol) via syringe. 19F NMR analysis at room temperature showed only the borane:imine adduct to be present (Figure 2a main text, full characterization of this compound will be reported in a forthcoming paper). Upon heating to 70 (C, 19F NMR analysis revealed only the ion-pair 1 to be present (Figure 2b) which remained as the predominant 19F containing species over a period of 90 minutes during which time 1H NMR confirmed hydrosilation was occurring. Characterization of Amines: All secondary amines from Table 1 are known compounds. Our 1H NMR spectra closely matched the literature data for all but one of the compounds (E6) for which no spectral data has previously been reported. E1: Nyasse, B.; Grehn, L.; Ragnarsson, U.; Maia, H. L. S.; Monteiro, L. S.; Leito, I.; Koppel, I.; Koppel, J. J. Chem. Soc. Perkin Trans. 1, 1995, 2025. E2: Wu, S.; Lee, S.; Beak, P. J. Am. Chem. Soc. 1996, 118, 715. E3, E4, E5: Chandrasekhar, S.; Reddy, M. V.; Chandraiah, L. Synth. Comm. 1999, 29, 3981. E6: 1H NMR (CDCl3, 200 MHz) 7.40-7.24 (m, 5H), 6.84-6.54 (m, 3H), 4.33 (s, 2H), 3.83 (s, 3H); 13C NMR (CDCl3, 50 MHz) 146.6, 139.5, 138.0, 128.4, 127.3, 126.9, 121.3, 116.7, 110.2, 109.5, 55.4, 48.1; IR (neat, NaCl, cm-1) 3418 (br.), 3064, 2937, 1596, 1509, 1446. See also, Wolfe, J.P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1158 and references therein. E7: Henke, B.; Kouklis, A. J.; Heathcock, C. H. J. Org. Chem. 1992, 57, 7056. E8: no product formed E9: Pak, C. S.; Kim, T. H.; Ha, S. J. J. Org. Chem. 1998, 63, 10006. E10: Froyen, P.; Juvvik, P. Tetrahedron Lett. 1995, 36, 9555. E11: Ranu, B. C.; Majee, A.; Sarkar, A. J. Org. Chem. 1998, 63, 370. E12: Tomaszewski, M. J.; Warkentin, J.; Werstiuk, N. H. Aust. J. Chem. 1995, 48, 291. E13: Mehrotra, K. N.; Giri, B. P. Synthesis 1977, 470.  Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics, 1996, 15, 1518. "%&'()*fgklyz^_bdjl56AB ! 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