Supporting Information. for

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1 Supporting Information for Structural and Electronic Noninnocence of -Diimine Ligands on Niobium for Reductive C Bond Activation and Catalytic Radical Addition Reactions Haruka Nishiyama, a Hideaki Ikeda, a Teruhiko Saito, a Benjamin Kriegel, b Hayato Tsurugi,* a John Arnold,* b and Kazushi Mashima* a a Department of Chemistry, Graduate School of Engineering Science, Osaka University b Department of Chemistry, University of California, Berkeley * tsurugi@chem.es.osaka-u.ac.jp (H.T.), arnold@berkeley.edu (J.A.), mashima@chem.es.osaka-u.ac.jp (K.M.) Contents: 1. Molecular structure of complexes 1b and 6b 2. VT-NMR measurement of 1a in toluene 3. Kinetic study for radical addition reaction 4. Synthesis of anionic niobium complexes, [ n Bu4N][Nb4( -diimine)] (5) 5. UV-vis spectra of complexes 1a and 5a in hexane 6. UV-vis spectra of complexes 1a, 6a, and 7a in benzene 7. UV-vis spectra of complex 1a in various solvents 8. ESR spectra of complexes 6a and 6b 9. Product data for radical addition reaction 10. X-ray crystallographic analysis 11. References S1

2 1. Molecular structure of complexes 1b and 6b Figure S1. Molecular structure of 1b with 50% thermal ellipsoids. All hydrogen atoms are omitted for clarity. Selected bond distances (Å) and angles (deg.): Nb N1, 1.990(6); Nb N2, 1.995(6); Nb 1, 2.389(2); Nb 2, 2.284(2); Nb 3, 2.386(2); Nb C1, 2.424(8); Nb C2, 2.425(7); N1 C1, 1.348(10); N2 C2, 1.363(10); C1 C2, 1.405(11); N1 Nb N2, 85.6(2); dihedral angle between N1 C1 C2 N2 and N1 Nb N2 planes, 121.8(3). S2

3 Figure S2. Molecular structure of 6b with 50% thermal ellipsoids. All hydrogen atoms are omitted for clarity. Selected bond distances (Å) and angles (deg.): Nb N1, 2.387(5); Nb N2, 2.393(5); Nb 1, (16); Nb 2, 2.139(4); Nb 3, 2.136(4); Nb 4, (15); N1 C1, 1.283(7); N2 C2, 1.281(7); C1 C2, 1.482(8); N1 Nb N2, 70.57(14); N1 Nb 1, 83.80(11); N1 Nb 2, 97.32(15); dihedral angle between N1 C1 C2 N2 and N1 Nb N2 planes, 171.7(3). S3

4 2. VT-NMR measurement of 1a in toluene We measured 1 H NMR spectra of 1a at different temperatures (Figure S3). The 1 H NMR spectrum of 1a in toluene-d8 at room temperature showed a singlet peak at 1.85 ppm for MeC=CMe, while only the peak was shifted to 1.53 ppm at -80 ºC, suggesting that there was a small contribution of the singlet/triplet niobium complexes, Nb(IV) species having -diimine monoanionic ligands ºC * -60 ºC * -40 ºC * -20 ºC * 0 ºC * 30 ºC CH(CH 3 ) 2 NC(CH 3 )=C(CH 3 )N * CH(CH 3 ) 2 Figure S3. Variable temperature 1 H NMR experiments for 1a. S4

5 3. Kinetic study for radical addition In a glovebox under argon, complex 1a, styrene, C4, and hexamethylbenzene as an internal standard were dissolved in C6D6 to set a total volume of 0.5 ml, and the solutions were transferred to J-young NMR tubes. The yield of the product was determined by integral ratios of signals for hexamethylbenzene and PhCHCH2C3 in the 1 H NMR spectra (Figures S4- S7, S9, and S11). Figure S4. Plot for the radical addition of C4 to styrene at different concentrations of 1a as the catalyst. Reaction condition: [styrene]0 = 0.60 M, [C4]0 = 3.0 M, temperature 100 ºC, [concentration of catalyst (mm) : kobs (s -1 )] = [18 : 5.22 x 10-5 ], [30 : 8.79 x 10-5 ], [36 : 1.05 x 10-4 ], [42 : 1.35 x 10-4 ], [60 : 1.89 x 10-4 ], [72 : 2.36 x 10-4 ]. S5

6 Figure S5. Plot for the radical addition of C4 to styrene at different concentrations of styrene. Reaction condition: [1a]0 = 18 mm, [C4]0 = 4.5 M, temperature 100 ºC, [concentration of styrene (M) : kobs (s -1 )] = [0.20 : 2.62 x 10-6 ], [0.30 : 5.31 x 10-6 ], [0.40 : 6.74 x 10-6 ], [0.60 : 8.89 x 10-6 ], [0.90 : 1.26 x 10-5 ], [1.2 : 1.19 x 10-5 ], [1.5 : 1.04 x 10-5 ], [1.8 : 9.38 x 10-6 ]. S6

7 Figure S6. Plot for the radical addition of C4 to styrene at different concentrations of C4. Reaction condition: [1a]0 = 18 mm, [styrene]0 = 0.60 M, temperature 100 ºC, [concentration of C4 (M) : kobs (s -1 )] = [2.4 : 6.05 x 10-6 ], [3.0 : 7.55 x 10-6 ], [3.6 : 8.87 x 10-6 ], [4.2 : 9.93 x 10-6 ], [4.8 : 1.11 x 10-5 ], [5.4 : 1.15 x 10-5 ], [6.0 : 1.17 x 10-5 ], [6.6 : 1.18 x 10-5 ]. We examined that activation parameters for the radical addition reaction were determined based on the temperature dependence of the reaction rate under the initial substrate concentrations of [1a] = 18 mm, [styrene]0 = 0.60 M, and [C4]0 = 3.0 M. Figures S7 and S8 show a standard Eyring plot for the temperature range from 73 to 92 C, giving ΔH = 10.3(1) kcal/mol, ΔS = -51.7(3) e.u., and ΔG (298 K) = 25.7(1) kcal/mol. The negative value of the activation entropy suggested the formation of the activated complex involving several components for the rate-determining step. S1 Figure S7. Plot for the radical addition of C4 to styrene at different temperatures. Reaction condition: [1a]0 = 18 mm, [styrene]0 = 0.60 M, [C4]0 = 3.0 M, [temperature (ºC) : kobs (s -1 )] = [73 : 1.16 x 10-5 ], [78 : 1.55 x 10-5 ], [83 : 1.71 x 10-5 ], [87 : 2.13 x 10-5 ], [92 : 2.74 x 10-5 ]. S7

8 Figure S8. Eyring plot for the radical addition reaction of C4 and styrene catalyzed by 1a. Reaction conditions: [1a]0 = 18 mm, [styrene]0 = 0.60 M, [C4]0 = 3.0 M. We also carried out kinetic experiments for the radical addition reaction of C4 to 1- octene or trimethyl(vinyl)silane catalyzed by 1a at 100 ºC in C6D6 with different concentrations of alkenes by using the same method as styrene. In the case of 1-octene, volcano-shape rate dependence was similarly observed (Figures S9 and S10). Similar deviation from the linearity of the alkene concentration was observed for trimethyl(vinyl)silane: the rate was gradually deviated from the linearity when more than 0.60 M of [alkene]0 was used, even though the volcano-shape rate dependence was not observed (Figures S11 and S12). S8

9 Figure S9. Plot for the radical addition of C4 to 1-octene at different concentrations of 1- octene. Reaction condition: [1a]0 = 18 mm, [C4]0 = 4.5 M, temperature 100 ºC, [concentration of 1-octene (M) : kobs (s -1 )] = [0.20 : 3.77 x 10-5 ], [0.30 : 8.33 x 10-5 ], [0.40 : 1.03 x 10-4 ], [0.60 : 1.25 x 10-4 ], [0.90 : 1.32 x 10-4 ], [1.2 : 1.25 x 10-4 ], [1.5 : 1.09 x 10-4 ], [1.8 : 6.16 x 10-5 ]. Figure S10. Dependence of kobs on the concentration of 1-octene for the radical addition reaction of C4 and 1-octene. Reaction condition: [1a]0 = 18 mm, [C4]0 = 4.5 M, temperature 100 ºC. S9

10 Figure S11. Plot for the radical addition of C4 to trimethyl(vinyl)silane at different concentrations of trimethyl(vinyl)silane. Reaction condition: [1a]0 = 18 mm, [C4]0 = 4.5 M, temperature 100 ºC, [concentration of trimethyl(vinyl)silane (M) : kobs (s -1 )] = [0.20 : 3.75 x 10-5 ], [0.30 : 5.41 x 10-5 ], [0.40 : 6.55 x 10-5 ], [0.60 : 1.04 x 10-4 ], [0.90: 1.30 x 10-4 ], [1.2 : 1.38 x 10-4 ], [1.5 : 1.45 x 10-4 ], [1.8 : 6.16 x 10-5 ]. Figure S12. Dependence of kobs on the concentration of trimethyl(vinyl)silane for the radical addition reaction of C4 and trimethyl(vinyl)silane. Reaction condition: [1a]0 = 18 mm, [C4]0 = 4.5 M, temperature 100 ºC. 4. Synthesis of anionic niobium complexes, [ n Bu4N][Nb4( -diimine)] (5) S10

11 We synthesized anionic niobium complexes, [ n Bu4N][Nb4( -diimine)] (5a:, -diimine = L1; 5b: -diimine = L2) (S1), to compare the structure and electronic characteristics of the -diimine ligand in 1, species A, and B. These complexes were characterized by 1 H and 13 C{ 1 H} NMR measurements as well as X-ray analysis (Figure S13). N N Ar Ar + n Bu 4 N Nb R R toluene, rt, 16 h 1 R R Ar N N Ar Nb n Bu 4 N 5a: R = Me (87% yield) 5b: R = H (93% yield) (S1) Figure S13. Molecular structure of 5b with 50% thermal ellipsoids. All hydrogen atoms and cationic part are omitted for clarity. Selected bond distances (Å) and angles (deg.): Nb N1, 2.088(3); Nb N2, 2.103(3); Nb 1, (9); Nb 2, (9); Nb 3, (9); Nb 4, (10) ;N1 C1, 1.374(4); N2 C2, 1.378(4); C1 C2, 1.351(5); N1 Nb N2, 74.16(10); dihedral angle between N1 C1 C2 N2 and N1 Nb N2 planes, A solution of 1a (100 mg, mmol) in toluene (10 ml) was added to a solution of n Bu4N (46.0 mg, mmol) in toluene (10 ml) at room temperature. The color of the S11

12 solution changed to orange. The reaction mixture was stirred for 16 h, and then all volatiles were removed under reduced pressure to orange solid. The precipitate was extracted with toluene (2 20 ml), and then all volatiles were removed under reduced pressure to orange solid. The solid was washed with hexane (3 10 ml). The remaining solid was dried to give 5a as orange powder in 87% yield (127 g, mmol), mp ºC (dec). 1 H NMR (400 MHz, C6D6, 303 K) δ 0.84 (t, 3 JHH = 6.8 Hz, 12H, N(CH2)3CH3), 1.19 (d, 3 JHH = 7.2 Hz, 12H, CH(CH3)2), (m, 16H, NCH2CH2CH2CH3), 1.76 (d, 3 JHH = 6.8 Hz, 12H, CH(CH3)2), 2.29 (s, 6H, NC(CH3)), (m, 8H, NCH2CH2CH2CH3), 4.57 (sept, 3 JHH = 6.8 Hz, 4H, CH(CH3)2), (m, 6H, aromatic protons). 13 C{ 1 H} NMR (100 MHz, C6D6, 303 K) δ 13.9 (N(CH2)3CH3), 14.9 (N=C(CH3)), 19.8 (NCH2CH2CH2CH3), 24.1 (NCH2CH2CH2CH3), 26.0 (CH(CH3)2), 26.1 (CH(CH3)2), 28.4 (CH(CH3)2), 58.6 (NCH2CH2CH2CH3), (m-ar), (NCH), (p-ar), (o-ar), (ipso-ar). A satisfactory elemental analysis could not be obtained due to decomposition of 5a during the isolation: anal. Calcd for C44H764N3Nb: C, 59.93; H, 8.69; N, Found: C, 58.63; H, 8.24; N, λmax/nm (ε/m - 1 cm -1 ): 344 ( ), 468 ( ). Complex 5b was prepared in similar manner as 5a. Orange powder was obtained in 93% yield, ºC (dec). 1 H NMR (400 MHz, C6D6, 303 K) δ 0.80 (t, 3 JHH = 6.8 Hz, 12H, N(CH2)3CH3), (m, 16H, NCH2CH2CH2CH3), 1.28 (d, 3 JHH = 7.2 Hz, 12H, CH(CH3)2), 1.73 (d, 3 JHH = 6.8 Hz, 12H, CH(CH3)2), (m, 8H, NCH2CH2CH2CH3), 4.58 (s, 2H, NCH), 4.89 (sept, 3 JHH = 6.8 Hz, 4H, CH(CH3)2), (m, 6H, aromatic protons). 13 C{ 1 H} NMR (100 MHz, C6D6, 303 K) δ 14.0 (N(CH2)3CH3), 20.0 (NCH2CH2CH2CH3), 24.3 (NCH2CH2CH2CH3), 24.6 (CH(CH3)2), 27.1 (CH(CH3)2), 28.4 (CH(CH3)2), 58.8 (NCH2CH2CH2CH3), (m-ar), (NCH), (p-ar), (o-ar), (ipso-ar). Anal. Calcd for C42H724N3Nb: C, 59.09; H, 8.50; N, Found: C, 58.78; H, 8.42; N, λmax/nm (ε/m -1 cm -1 ): 334 ( ), 453 ( ). 5. UV-vis spectra of complexes 1a and 5a in hexane S12

13 Figure S14. UV-vis spectra of 1a and 5a in hexane at room temperature. 6. UV-vis spectra of complexes 1a, 6a, and 7a in benzene Figure S15. UV-vis spectra of 1a, 6a, and 7a in benzene at room temperature. 7. UV-vis spectrum of complexes 1a in various solvents S13

14 Figure S16. UV-Vis spectra of complex 1a in styrene (green trace), fluorobenzene (blue trace), and benzene (red trace). 8. ESR spectra of complexes 6a and 6b The ESR spectrum of 6a displayed a ten-line splitting signal due to the 9/2 nuclear spin of 93 Nb (g = 1.918, Aiso = 105 G) (Figure S17a), which was consistent with a simulation spectrum as a niobium-centered radical (anb = 105 G) (Figure S17b). In contrast, the ESR spectrum for 6b showed a nine-line with a much weaker hyperfine coupling constant consistent with an organic radical (g = 2.003, Aiso = 6.56 G) (Figure S18a). This was simulated by taking into account hyperfine coupling with two virtually identical nitrogen atoms (an = 6.80 G) and four equivalents hydrogen atoms of N=CH as well as the para-hydrogen atom of the N-aryl group (ah = 6.31 G) (Figure S18b). S14

15 Figure S17. (a) ESR spectrum in toluene at room temperature for 6a (blue line) and (b) simulated spectrum of 6a (red line). Figure S18. (a) ESR spectrum in toluene at room temperature for 6b (blue line) and (b) simulated spectrum of 6b (red line). 9. Product data for radical addition (1,3,3,3-Tetrachloropropyl)benzene (4a) S2 1 H NMR (400 MHz, 303 K, CD3): 3.55 (dd, 3 JH-H = 6.0 Hz, 2 JH-H = 15.4 Hz, 1H, 3CCHH), 3.63 (dd, 3 JH-H = 6.0 Hz, 2 JH-H = 15.4 Hz, 1H, 3CCHH), 5.31 (t, 3 JH-H = 6.0 Hz, 1H, -CH()-), (m, 5H, Ph). 13 C{ 1 H} NMR (100 MHz, 303 K, CD3): HRMS(EI + ): m/z calcd. for C9H Found S15

16 1-Methyl-4-(1,3,3,3-tetrachloropropyl)benzene (4b) S2 1 H NMR (400 MHz, 303 K, CD3): 2.41 (s, 3H, p-me), 3.67 (dd, 3 JH-H = 4.7 Hz, 2 JH-H = 16.0 Hz, 1H, 3CCHH), 3.65 (dd, 3 JH-H = 4.7 Hz, 2 JH-H = Me 16.0 Hz, 1H, 3CCHH), 5.34 (t, 3 JH-H = 4.7 Hz, 1H, -CH()-), (m, 5H, Ph). 13 C{ 1 H} NMR (100 MHz, 303 K, CD3): HRMS(EI + ): m/z calcd. for C10H Found Chlro-4-(1,3,3,3-tetrachloropropyl)benzene (4c) S2 1 H NMR (400 MHz, 303 K, CD3): 3.60 (dd, 3 JH-H = 6.2 Hz, 2 JH-H =15.0 Hz, 1H, 3CCHH), 3.50 (dd, 3 JH-H = 6.2 Hz, 2 JH-H =15.0 Hz, 1H, 3CCHH), 5.28 (t, 3 JH-H = 6.2 Hz, 1H, -CH()-), (m, 4H, Ar). 13 C{ 1 H} NMR (100 MHz, 303 K, CD3): HRMS(EI + ): m/z calcd. for C9H found (1,3,3,3-Tetrachloropropyl)-4-(trifluoromethyl)benzene (4d) S2 1 H NMR (400 MHz, 303 K, CD3): 3.53 (dd, 3 JH-H = 6.2 Hz, 2 JH-H =15.5 Hz, 1H, 3CCHH), 3.63 (dd, 3 JH-H = 6.2 Hz, 2 JH-H =15.5 Hz, 1H, F 3 C 3CCHH), 5.34 (t, 3 JH-H = 6.2 Hz, 1H, -CH()-), (m, 4H, Ar). 13 C{ 1 H} NMR (100 MHz, 303 K, CD3): (q, 3 JC-F = 3.7 Hz) (q, 1 JC-F = 271 Hz) (q, 2 JC-F = 32.3 Hz) 19 F{ 1 H} NMR (376 MHz, 303 K, CD3): HRMS(EI + ): m/z calcd. for C10H7F Found Methyl-3-(1,3,3,3-tetrachloropropyl)benzene (4e) 1 H NMR (400 MHz, 303 K, CD3): 2.34 (s, 3H, m-me), 3.63 (dd, 3 JH-H = Me 6.0 Hz, 2 JH-H =16.0 Hz, 1H, 3CCHH), 3.55 (dd, 3 JH-H = 6.0 Hz, 2 JH-H =16.0 S16

17 Hz, 1H, 3CCHH), 5.29 (t, 3 JH-H = 6.0 Hz, 1H, -CH()-), (m, 4H, Ar). 13 C{ 1 H} NMR (100 MHz, 303 K, CD3): HRMS(EI + ): m/z calcd. for C10H Found ,1,1,3-Tetrachlorononane (4g) S3 1 H NMR (400 MHz, 303 K, CD3): 0.89 (t, 3 JH-H =6.8 Hz, 3H, CH3CH2), (m, 6H, CH3CH2CH2CH2), (m, 2H, CH2CH2CH()), (m, 2H, n Hex CH2CH()), 3.12 (dd, 3 JH-H = 4.9 Hz, 2 JH-H =15.7 Hz, 1H, 3CCHH), 3.27 (dd, 3 JH-H = 4.9 Hz, 2 JH-H =15.7 Hz, 1H, 3CCHH), (m, 1H, -CH()-). 13 C{ 1 H} NMR (100 MHz, 303 K, CD3): HRMS(EI + ): m/z calcd. for C9H Found S17

18 Trimethyl(1,3,3,3-tetrachloropropyl)silane (4h) 1 H NMR (400 MHz, 303 K, CD3): 0.19 (s, 9H, Me3Si), (m, 2H, 3CCH2), (m, 1H, -CH()-). 13 C{ 1 H} NMR (100 MHz, 303 K, Me 3 Si CD3): HRMS(EI + ): m/z calcd. for C6H124Si Found (1,3,3,3-Tetrachloropropyl)cyclohexane (4i) S4 1 H NMR (400 MHz, 303 K, CD3): (m, 5H, Cy), (m, 6H, Cy), (m, 2H, 3CCH2), (m 1H, -CH()-). 13 C{ 1 H} NMR (100 MHz, Cy 303 K, CD3): HRMS(EI + ): m/z calcd. for C9H found (2,4,4,4-Tetrachlorobutyl)benzene (4j) S5 1 H NMR (400 MHz, 303 K, CD3): (m, 4H, CH2CH()CH2), (m, 1H, -CH()-), (m, 5H, Ph), 3.55 (dd, 3 JH-H = 5.5 Hz, 2 JH-H = 15.4 Hz, 1H, 3CCHH). 13 C{ 1 H} NMR (100 MHz, 303 K, CD3): HRMS(EI + ): m/z calcd. for C10H Found S18

19 Figure S19. 1 H and 13 C{ 1 H} NMR spectra of (1,3,3,3-tetrachloropropyl)benzene (4a). S19

20 Me Figure S20. 1 H and 13 C{ 1 H} NMR spectra of 1-methyl-4-(1,3,3,3-tetrachloropropyl)benzene (4b). S20

21 Figure S21. 1 H and 13 C{ 1 H} NMR spectra of 1-chlro-4-(1,3,3,3-tetrachloropropyl)benzene (4c). S21

22 F 3 C Figure S22. 1 H and 13 C{ 1 H} NMR spectra of 1-(1,3,3,3-Tetrachloropropyl)-4- (trifluoromethyl)benzene (4d). S22

23 Me Figure S23. 1 H and 13 C{ 1 H} NMR spectra of 1-methyl-3-(1,3,3,3-tetrachloropropyl)benzene (4e). S23

24 n Hex Figure S24. 1 H and 13 C{ 1 H} NMR spectra of 1,1,1,3-tetrachlorononane (4g). S24

25 Me 3 Si Figure S25. 1 H and 13 C{ 1 H} NMR spectra of trimethyl(1,3,3,3-tetrachloropropyl)silane (4h). S25

26 Cy Figure S26. 1 H and 13 C{ 1 H} NMR spectra of (1,3,3,3-tetrachloropropyl)cyclohexane (4i). S26

27 Figure S27. 1 H and 13 C{ 1 H} NMR spectra of (2,4,4,4-tetrachlorobutyl)benzene (4j). S27

28 10. X-ray crystallographic analysis Table S1. Crystallographic and refinement data for 1a, 1b, 5b, 6a, and 6b. 1a Formula C28H403N2Nb C26H363N2Nb Mw, g.mol Cryst size, mm Crystal color and habit red block orange prism Cryst syst. monoclinic monoclinic Space group P21/n P21/n T, K 113(2) 113(2) a, Å (3) (10) b, Å (4) (11) c, Å, degree (3) (2) - β, degree, degree (19) (5) - V, Å (12) (5) Z 4 4 Dcalcd, g cm μ(mo Kα), mm F(000) θ range, deg Reflns collected Indep reflns (Rint) 6685 (0.0178) 6282 (0.0764) Reflns obsd [I > 2 (I)] Data/restraints/params 6685/0/ /0/279 R1, wr2 [I > 2σ(I)] , , R1, wr2 (all data) , , Goodness-of-fit on F Δρmax, min, e Å , , a) R1 = ( Fo - Fc )/( Fo ) b) wr2 = [{ w(fo 2 -Fc 2 ) 2 }/{ w(fo 2 ) 2 }] 1/2 1b S28

29 Table S1. Crystallographic and refinement data for 1a, 1b, 5b, 6a, and 6b (continue). 5b Formula C42H724N3Nb C28H404N2Nb Mw, g.mol Cryst size, mm Crystal color and habit yellow block green block Cryst syst. monoclinic triclinic Space group P21/n P1 T, K 113(2) 113(2) a, Å (12) (8) b, Å (8) (9) c, Å, degree (3) (10) (3) β, degree, degree (4) (3) (3) V, Å (7) (12) Z 4 1 Dcalcd, g cm μ(mo Kα), mm F(000) θ range, deg Reflns collected Indep reflns (Rint) (0.0305) 6252 (0.1234) Reflns obsd [I > 2 (I)] Data/restraints/params 10604/0/ /3/326 R1, wr2 [I > 2σ(I)] , , R1, wr2 (all data) , , Goodness-of-fit on F Δρmax, min, e Å , , a) R1 = ( Fo - Fc )/( Fo ) b) wr2 = [{ w(fo 2 -Fc 2 ) 2 }/{ w(fo 2 ) 2 }] 1/2 6a S29

30 Table S1. Crystallographic and refinement data for 1a, 1b, 5b, 6a, and 6b (continue). Formula 6b Mw, g.mol C26H364N2Nb Cryst size, mm Crystal color and habit Cryst syst. Space group brown block triclinic P1 T, K 113(2) a, Å (9) b, Å (9) c, Å (15), degree (18) β, degree (3), degree (3) V, Å (4) Z 4 Dcalcd, g cm μ(mo Kα), mm F(000) 1260 θ range, deg Reflns collected Indep reflns (Rint) (0.0612) Reflns obsd [I > 2 (I)] Data/restraints/params 12755/0/611 R1, wr2 [I > 2σ(I)] , R1, wr2 (all data) , Goodness-of-fit on F Δρmax, min, e Å , a) R1 = ( Fo - Fc )/( Fo ) b) wr2 = [{ w(fo 2 -Fc 2 ) 2 }/{ w(fo 2 ) 2 }] 1/2 S30

31 11. References (S1) Eckenhoff, W. T.; Biernesser, A. B.; Pintauer, T. Inorg. Chem. 2012, 51, (S2) Oe, Y.; Uozumi, Y. Adv. Synth. Cat. 2008, 350, (S3) Mitani, M,; Kiriyama, T.; Kuratate, T. J. Org. Chem. 1994, 59, (S4) Francois, H.; Derion, B.; Lalande, R. Bull. Soc. Chim. Fr. 1970, 617. (S5) Akiyama, T.; Yoshida, Y.; Hanawa, T.; Sugimori, A. Bull. Chem. Soc. Jpn. 1983, 56, S31