Hassan Osseili, Debabrata Mukherjee, Klaus Beckerle, Thomas P. Spaniol, and Jun Okuda*

Transcription

1 Supporting Information Me6TREN-Supported Alkali Metal Hydridotriphenylborates [(L)M][HBPh3] (M = Li, Na, K): Synthesis, Structure, and Reactivity Hassan Osseili, Debabrata Mukherjee, Klaus Beckerle, Thomas P. Spaniol, and Jun Okuda* Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, Aachen, Germany Table of Contents Spectroscopic data for compounds S2 Spectroscopic data for 1-d...S11 Variable temperature NMR analysis of 1...S14 Line shape analysis and Eyring Plot...S17 Spectroscopic data for B(C 6 H 4 -p-me) 3 and B(C 6 H 4 -p-cf 3 ) 3...S20 Spectroscopic data for compounds 8 and 9...S22 Hydroboration catalysis...s28 X-ray Crystallography...S31 References...S32 S1

2 Spectroscopic data for compounds 4-7. [(L)Li][Ph 3 B N(SiHMe 2 ) 2 ] (4). Figure S1. 1 H NMR spectrum of 4 in THF-d 8. Figure S2. 13 C{ 1 H} NMR spectrum of 4 in THF-d 8. S2

3 Figure S3. 11 B NMR spectrum of 4 in THF-d 8. Figure S4. 29 Si{ 1 H} NMR spectrum of 4 in THF-d 8. S3

4 Figure S5. 7 Li{ 1 H} NMR spectrum of 4 in THF-d 8. [(L)Na][Ph 3 B N(SiHMe 2 ) 2 ] (5). Figure S6. 1 H NMR spectrum of 5 in THF-d 8. S4

5 Figure S7. 13 C{ 1 H} NMR spectrum of 5 in THF-d 8. Figure S8. 11 B NMR spectrum of 5 in THF-d 8. S5

6 Figure S9. 29 Si{ 1 H} NMR spectrum of 5 in THF-d 8. [(L)K][Ph 3 B N(SiHMe 2 ) 2 ] (6). Figure S10. 1 H NMR spectrum of 6 in THF-d 8. S6

7 Figure S C{ 1 H} NMR spectrum of 6 in THF-d 8. Figure S B NMR spectrum of 6 in THF-d 8. S7

8 Figure S Si{ 1 H}NMR spectrum of 6 in THF-d 8. ν (cm 1 ) Figure S14. FT-IR spectrum (KBr) of 6. S8

9 [(L)Li][Ph 3 B OCHPh 2 ] (7). Figure S15. 1 H NMR spectrum of 7 in THF-d 8. Figure S C{ 1 H} NMR spectrum of 7 in THF-d 8. S9

10 Figure S B NMR spectrum of 7 in THF-d 8. Figure S18. 7 Li{ 1 H} NMR spectrum of 7 in THF-d 8. S10

11 ν (cm 1 ) Figure S19. FT-IR spectrum (KBr) of 7. Spectroscopic data for 1-d. Figure S20. 1 H NMR spectrum of 1-d in THF-d 8. S11

12 Figure S21. 2 H{ 1 H} NMR spectrum of 1-d in THF. Benzene-d 6 was used as a reference. Figure S C{ 1 H} NMR spectrum of 1-d in THF-d 8. S12

13 Figure S B NMR spectrum of 1-d in THF-d 8. Figure S24. 7 Li{ 1 H} NMR spectrum of 1-d in THF-d 8. S13

14 ν (cm 1 ) Figure S25. FT- IR spectrum (KBr) of 1-d. Variable temperature NMR analysis of 1. Two-dimensional 1 H- 15 N HMBC and 1 H- 13 C HSQC NMR spectra of 1 were acquired in THFd8 to assign the 1 H and 13 C NMR chemical shifts to the N-methyl and methylene groups of N(CH2CH2NMe2)3 (L) ligand. Figure S26. 1 H- 15 N HMBC NMR spectrum of 1 in THF-d 8. S14

15 Figure S27. 1 H- 13 C HSQC NMR spectrum of 1 in THF-d 8. Figure S28. Variable temperature 1 H NMR spectra of 1 in THF-d 8. S15

16 Figure S29. Variable temperature 13 C{ 1 H} NMR spectra of 1 in THF-d 8. Figure S30. Variable temperature 13 C{ 1 H} NMR spectra of 1 in THF-d 8 showing only the L region. S16

17 Figure S31. 1 H NMR spectra of a recrystallized and gently dried sample of 1 at 298 K and 233 K. Line shape analysis and Eyring plot. Line shape analysis was performed with Bruker Topspin The analysis is based on a model placing two spins ½ at ppm (experimental low temperature limit of the signal from carbon c ) and ppm (chemical shifts of the free ligand; assumed as high temperature limit) in two independent molecules. Two reactions were defined, exchanging spin 1 to spin 2 and vice versa with stoichiometric coefficients -1 and 1 respectively. Exchange rate and molar fraction X1 were adjusted manually to give the best overlap. The resulting simulated spectra are shown in Figure S5 and the results are summarized in Table S1. S17

18 Figure S32. Experimental (blue) and simulated (green) 13 C{ 1 H} NMR spectra from line shape analysis of 1. The red bar marks the refined area. S18

19 Table S1. Results of line shape analysis for the experimental spectra of [(L)Li][HBPh 3 ]. Temperature ( C) Exchange rate k (Hz) Molar fraction X1 Overlap (%) An Eyring plot derived from the above analysis provides the activation parameters as H = 13.3±0.9 kcal mol 1 and S = 5.2±0.3 cal mol 1 K 1 that lead to G 298K = 11.8±0.9 kcal mol 1 at 298 K. Figure S33. Eyring plot of the exchange rates from D-NMR simulation. S19

20 Spectroscopic data for B(C6H4-p-Me)3 and B(C6H4-p-CF3)3. B(C 6 H 4 -p-me) 3. Figure S34. 1 H NMR spectrum of B(C 6 H 4 -p-me) 3 in benzene-d 6. Figure S B NMR spectrum of B(C 6 H 4 -p-me) 3 in benzene-d 6. S20

21 B(C 6 H 4 -p-cf 3 ) 3. Figure S36. 1 H NMR spectrum of B(C 6 H 4 -p-cf 3 ) 3 in benzene-d 6. Figure S B NMR spectrum of B(C 6 H 4 -p-cf 3 ) 3 in benzene-d 6. S21

22 Figure S F NMR spectrum of B(C 6 H 4 -p-cf 3 ) 3 in benzene-d 6. Spectroscopic data for compounds 8 and 9. [(L)Li][HB(C 6 H 4 -p-me) 3 ] (8). Figure S39. 1 H NMR spectrum of 8 in THF-d 8. S22

23 Figure S C{ 1 H} NMR spectrum of 8 in THF-d 8. Figure S B NMR spectrum of 8 in THF-d 8. S23

24 Figure S42. 7 Li{ 1 H} NMR spectrum of 8 in THF-d 8. ν (cm 1 ) Figure S43. FT- IR spectrum (KBr) of 8. S24

25 [(L)Li][HB(C 6 H 4 -p-cf 3 ) 3 ] (9). Figure S44. 1 H NMR spectrum of 9 in THF-d 8. Figure S C{ 1 H} NMR spectrum of 9 in THF-d 8. S25

26 Figure S B NMR spectrum of 9 in THF-d 8. Figure S F NMR spectrum of 9 in THF-d 8. S26

27 Figure S48. 7 Li{ 1 H} NMR spectrum of 9 in THF-d 8. ν (cm 1 ) Figure S49. FT-IR spectrum (KBr) of 9. S27

28 Hydroboration catalysis. A J.Young-style NMR tube was charged with benzophenone (0.27 mmol), HBpin or DBpin (0.27 mmol), and 0.5 ml of a 3:1 mixture of THF and THF-d8. Desired catalyst loading was achieved by adding an appropriate volume of catalyst stock solution of known concentration in THF using a microliter syringe. Reaction progress was monitored at room temperature using NMR spectroscopy. The products were characterized by 1 H, 11 B, and 13 C NMR spectroscopies and compared with the literature. 2 Figure S50. 1 H NMR spectrum at the end (1.5 h) of catalytic hydroboration of benzophenone by HBpin in the presence of mol% of 1. S28

29 Figure S B NMR spectrum at the end (1.5 h) of catalytic hydroboration of benzophenone by HBpin in the presence of mol% of 1. Figure S52. 1 H NMR spectrum at the end (4 h) of catalytic hydroboration of benzophenone by DBpin in the presence of mol% of 1. S29

30 Figure S B NMR spectrum at the end (4 h) of catalytic hydroboration of benzophenone by DBpin in the presence of mol% of 1. Figure S54. Plot of % conversion vs. time for mol% of 1 catalyzed hydroboration of benzophenone by HBpin and DBpin, respectively. S30

31 X-ray Crystallography. The single-crystal X-ray diffraction measurements of 5-8 were performed at 100(2) K on a Bruker AXS diffractometer equipped with an Incoatec microsource and an APEX area detector using MoKα radiation (λ = Å), multilayer optics and ω-scans. Temperature control was achieved with an Oxford cryostream 700. The data reductions were performed with the Bruker SAINT software. 3 The Absorption corrections were carried out using the program SADABS. 4 The structures were solved by direct methods using the program SIR The crystal of 8 contained two crystallographically independent molecules in the lattice. All refinements was carried out by the full-matrix least squares method with anisotropic displacement parameters for all non-hydrogen atoms using SHELXL-2013 as implemented in the WinGX program system. 6,7 The hydrogen atoms H2 and H2 that are bound to silicon in 5, all hydrogen atoms in 6, and the hydrogen atom H1 that is bound to boron in 8 were located in Fourier difference maps and were refined in their position. All remaining hydrogen atoms were included as riding in calculated positions with Uiso(H) = 1.2Ueq(C) or 1.5Ueq.(non-H). Refinement results are given in Table S2. The graphical representation was obtained with the computer program DIAMOND. 8 CCDC (5), (6), (7), (8) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Crystallographic Data Centre via Figure S55. Structure of one crystallographically independent formula unit of 8. Displacement parameters are drawn at 50% probability. Hydrogen atoms except for the hydrogen atom bound to the boron atom are omitted for clarity. Table S2. Crystal data and structure refinement. chemical formula C 22 H 29 BNSi 2, C 16 H 38 N 4 NaO C 22 H 29 BNSi 2, C 12 H 30 KN 4 C 31 H 26 BO, C 16 H 38 LiN 4 O fw (g mol -1 ) space group P2 1 /c P2 1 /n P2 1 /n P2 1 C 16 H 38 LiN 4 O, C 21 H 22 B S31

32 crystal size (mm) unit cell parameters a (Å) (9) (6) (4) (4) b (Å) (13) (14) (3) (6) c (Å) (19) (9) (5) (6) α ( ) β ( ) (14) (10) (4) (7) γ ( ) V (Å 3 ) (6) (4) (18) 3647(2) Z T (K) 100(2) 100(2) 100(2) 100(2) µ(mo K α ) (mm -1 ) reflns independent reflns (R int. ) observed reflns 8580 (0.0566) 9491 (0.0511) 7818 (0.0967) (0.0851) parameters goodness of fit on F final R indices R1, wr2 [I 2σ(I)] R1, wr2 (all data) , , , , , , , , References. 1 Bruker, TopSpin 3.0, Bruker BioSpin, Billerica, Massachusetts, Mukherjee, D; Osseili, H.; Spaniol, T. P.; Okuda, J. J. Am. Chem. Soc. 2016, 138, Bruker, SAINT-Plus, Bruker AXS Inc., Madison, Wisconsin, USA, Bruker, SADABS, Bruker AXS Inc. Madison, Wisconsion, USA, Altomare, A; Cascarano, G.; Giacovazzo, C.; Guagliardi, A. J. Appl. Crystallogr. 1993, 26, Sheldrick, G. M. Acta Crystallogr. Sect. A 2008, 64, Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, Brandenburg, K. Diamond Version 3.2i, Crystal Impact GbR, Bonn, S32