Supporting Information

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1 Supporting Information Wiley-VCH Weinheim, Germany

2 Facile Heterolytic H 2 Activation by Amines and B(C 6 F 5 ) 3 Victor Sumerin, Felix Schulz, Martin Nieger, Markku Leskelä, Timo Repo,* and Bernhard Rieger* Prof. Dr. T. Repo, Department of Chemistry, University of Helsinki, P.O. Box 55, FIN-00014, Helsinki, Finland, Fax: (+358) , timo.repo@helsinki.fi Prof. Dr. Dr.h.c. B. Rieger, WACKER-Lehrstuhl für Makromolekulare Chemie, Technische Universität München, Lichtenbergstrasse 4, D-85747, Garching bei München, Germany, rieger@tum.de Materials and Methods: All experiments were performed on double-manifold H 2 (Ar)/vacuum lines or in an argon glove box (MBraun Labmaster 130). Solvents were dried by an MBraun solvent purification system (MB SPS-800). Hydrogen gas was purchased from AGA Ab and passed through a drying unit prior to use. All organic reagents were purchased from Acros Organics, Sigma-Aldrich or Strem and purified by conventional methods. NMR experiments were performed on a Bruker ARX-300 spectrometer ( 1 H, 13 C, 19 F) or Bruker DPX-400 ( 11 B). 1 H, 13 C NMR spectra are referenced to SiMe 4 by referencing the residual solvent peak. 11 B, 19 F NMR spectra were referenced externally to BF 3 *Et 2 O at 0 ppm and CF 3 CO 2 H at ppm relative to CFCl 3 at 0 ppm, respectively. The single-crystal X-ray diffraction study of 1c was carried out on a Bruker-Nonius Kappa-CCD diffractometer at 123(2) K using Mo Kα radiation (λ = Å). Direct Methods (SHELXS-97) were used for structure solution, and full-matrix leastsquares refinement on F 2 (SHELXL-97). H atoms were localized by difference Fourier synthesis and refined using a riding model. H(B, N) were refined free. The absolute structure could not be determined reliably (Flack s x-parameter: x = 0.1(4)). Crystallographic data (excluding structure factors) for the structure reported in this work have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC (1c). Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge DB2 1EZ, UK (Fax: int.code+(1223) ; deposit@ccdc.cam.ac.uk). Typical procedure: In a glove box, a 25-mL flame-dried Schlenk tube equipped with a stir bar, a Teflon stopcock and a cap (Glindemann -sealing rings were used for conical joints instead of grease) was charged with B(C 6 F 5 ) 3 (0.2 mmol, mg), 1 ml dry toluene and amine (0.2 mmol). The reaction was degassed once with a freeze-pump-thaw cycle and refilled with H 2 (1 atm). The reaction was stirred at 1000 rpm and at a suitable temperature for an 1 h. All volatiles were removed in vacuo to give the product as a white solid. Crystals suitable for X-Ray diffraction were grown from a layered toluene/pentane solution at 20ºC. [i-pr 2 NH 2 ][HB(C 6 F 5 ) 3 ] (1b) 1 H NMR (C 6 D 6, 300 MHz): δ 4.37 (pseudo br s, 2H, NH 2 ), δ 3.63 (br q, 1H, 1 J BH = 73 Hz, BH), δ 2.33 (m, 2H, CH), δ 0.46 (d, 12H, 1 J NH = 6.5 Hz, CH 3 ). 11 B NMR (C 6 D 6, 128 MHz): δ (d, 1 J BH = 83 Hz). 13 C NMR (C 6 D 6, 75 MHz): δ (dm, 1 J CF = 230 Hz, ortho-c 6 F 5 ), δ (dm, 1 J CF = 250 Hz, para-c 6 F 5 ), δ (dm, 1 J CF = 241 Hz, meta-c 6 F 5 ), δ (s, NCH(CH 3 ) 2 ), δ (s, NCH(CH 3 ) 2 ). Quaternary carbon of C 6 F 5 ring was not observed. 19 F NMR (C 6 D 6, 282 MHz): δ (d, 6F, 3 J FF = 20 Hz, ortho-c 6 F 5 ), δ (t, 3F, 3 J FF = 21 Hz, para-c 6 F 5 ), δ (m, 6F, meta-c 6 F 5 ). Anal. Calcd. for C 24 H 17 BF 15 N: C 46.86; H 2.79; N Found: C 47.39; H 2.61; N 2.38.

3 [C 9 H 18 NH 2 ][HB(C 6 F 5 ) 3 ] (1c) 1 H NMR (C 6 D 6, 300 MHz): δ 4.32 (br t (1:1:1), 2H, 1 J NH = 43 Hz, NH 2 ), δ 3.74 (br q, 1H, 1 J BH = 76 Hz, BH), δ 0.80 (m, 2H, CH 2 ), δ 0.71 (m, 4H, CH 2 ), δ 0.59 (s, 12H, CH 3 ). 11 B NMR (C 6 D 6, 128 MHz): δ (d, 1 J BH = 75 Hz) 13 C NMR (C 6 D 6, 75 MHz): δ (dm, 1 J CF = 238 Hz, ortho-c 6 F 5 ), δ (dm, 1 J CF = 241 Hz, para-c 6 F 5 ), δ (dm, 1 J CF = 251 Hz, meta-c 6 F 5 ), δ (s, NC(CH 3 ) 2 CH 2 ), δ (s, NC(CH 3 ) 2 CH 2 ), δ (s, NC(CH 3 ) 2 CH 2 ), δ (s, NC(CH 3 )2CH 2 CH 2 ). Quaternary carbon of C 6 F 5 ring was not observed. 19 F NMR (C 6 D 6, 282 MHz): δ (d, 6F, 3 J FF = 21 Hz, ortho-c 6 F 5 ), δ (t, 3F, 3 J FF = 20 Hz, para-c 6 F 5 ), δ (m, 6F, meta-c 6 F 5 ). Anal. Calcd. for C 27 H 21 BF 15 N: C 49.49; H 3.23; N Found: C 50.25; H 3.20; N : In a glove box, a 25-mL flame-dried Schlenk tube was charged with [C 9 H 18 NH 2 ][HB(C 6 H 5 ) 3 ] (1c) (0.15 mmol, 98.3 mg), 1 ml dry CH 2 Cl 2 and benzaldehyde (0.15 mmol, 15.9 mg). The reaction was stirred at 1000 rpm and at RT for 1 h. All volatiles were removed in vacuo to give the product as a white solid. [C 9 H 18 NH 2 ][PhCH 2 OB(C 6 F 5 ) 3 ] (3) 1 H NMR (DMSO-d 6, 300 MHz): δ 7.89 (br s, 2H, NH 2 ), δ 7.32 (d, 2H, 3 J HH = 7.4 Hz, ortho-arh) δ 7.21 (t, 2H, 3 J HH = 7.4 Hz, meta -ArH), δ 7.10 (t, H, 3 J HH = 7.1 Hz, para-arh), δ 4.18 (s, PhCH 2 ), δ 1.64 (m, 2H, CH 2 ), δ 1.51 (m, 4H, CH 2 ), δ 1.31 (s, 12H, CH 3 ). 11 B NMR (DMSO-d 6, 128 MHz): δ 1.58 (s) 13 C NMR (DMSO-d 6, 75 MHz): δ (dm, 1 J CF = 240 Hz, ortho-c 6 F 5 ), δ (s, quaternary carbon of C 6 H 5 ), δ (dm, 1 J CF = 245 Hz, para-c 6 F 5 ), δ (dm, 1 J CF = 243 Hz, meta-c 6 F 5 ), δ (s, meta-c 6 H 5 ), δ (s, ortho-c 6 H 5 ), ), δ (s, para-c 6 H 5 ), δ (s, PhCH 2 O), δ (s, NC(CH 3 ) 2 CH 2 ), δ (s, NC(CH 3 ) 2 CH 2 ), δ (s, NC(CH 3 ) 2 CH 2 ), δ (s, NC(CH 3 )2CH 2 CH 2 ). Quaternary carbon of C 6 F 5 ring was not observed. 19 F NMR (DMSO-d 6, 282 MHz): δ (d, 6F, 3 J FF = 21 Hz, ortho-c 6 F 5 ), δ (t, 3F, 3 J FF = 21 Hz, para-c 6 F 5 ), δ (m, 6F, meta-c 6 F 5 ). Anal. Calcd. for C 34 H 27 BF 15 NO: C 53.64; H 3.57; N Found: C 53.84; H 3.54; N 1.90.

4 Figure 1: N-H F and C-H F hydrogen bonds in 1c. Table 7. Hydrogen bonds for les031 [A and deg.]. D-H...A d(d-h) d(h...a) d(d...a) <(DHA) N(1)-H(1A)...F(22) 0.90(2) 2.07(3) 2.937(2) 163(2) N(1)-H(1B)...F(32)#1 0.92(2) 2.11(2) 3.007(2) 166.0(19) C(3)-H(3A)...F(25)# (3) C(5)-H(5A)...F(36)# (3) C(7)-H(7C)...F(12)# (3) Symmetry transformations used to generate equivalent atoms: #1 -x+2,y-1/2,-z+3/2 #2 -x+1,y-1/2,-z+3/2 #3 x+1/2,-y+3/2,-z+1

5 Figure 2. Crystal packing of 1c.

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