Supporting Information For: Brønsted Acid-Promoted Formation of Stabilized Silylium Ions for Catalytic Friedel Crafts C H Silylation

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1 Supporting Information For: Brønsted Acid-Promoted Formation of Stabilized Silylium Ions for Catalytic Friedel Crafts C H Silylation Qing-An Chen, Hendrik F. T. Klare, and Martin Oestreich* martin.oestreich@tu-berlin.de Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, Berlin, Germany Table of Contents 1. General...S1 2. The detection of stabilized silylium ion...s2 3. Typical procedure for C H silylation...s2-s3 4. Gram-scale synthesis of C-3 silylated indole...s3 5. Characterization data...s Molecular structure and X-ray data of compound 7ai...S References...S8 8. Copy of MR spectra...s General: Commercial reagents were purchased from Sigma Aldrich, Strem, or Alfa Aesar and used without further purification. Hydrosilanes were dried over CaH 2 and distilled prior to use. [H(OEt 2 ) 2 ] + [BAr F 4] were prepared according to reported procedures. 1 Toluene (HPLC grade) for the electrophilic aromatic substitution reactions was dried over sodium, distilled, degassed with three freeze-pump-thaw cycles, and stored in a glovebox. Technical grade solvents for extraction or chromatography (TBME, cyclohexane, ethyl acetate, and Et 3 ) were distilled prior to use. Reactions were generally performed inside an MBraun glove box under a static pressure of argon unless otherwise stated. Analytical thin layer chromatography (TLC) was performed on silica gel 60 F254 glass plates by rck. Flash column chromatography was performed on silica gel 60 (40 63 μm, mesh, ASTM) using the indicated solvents. 1 H, 13 C, 19 F, and 29 Si MR spectra were recorded in CDCl 3, d 6 -acetone, C 6 D 6, or 1,2-Cl 2 C 6 D 4 on Bruker AV500 instrument. Chemical shifts are reported in parts per million (ppm) and are referenced to the residual solvent resonance as the internal standard (CHCl 3 : δ = 7.26 ppm for 1 H MR and CDCl 3 : δ = ppm for 13 C MR). Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplett, q = quartet, sept = septet, m = multiplet, br = broad signal), coupling constants (Hz), and integration. Gas liquid chromatography (GLC) was performed on an Agilent Technologies 7820A gas chromatograph equipped with a FS-SE-54 capillary column (30 m 0.32 mm, 0.25 μm film thickness). Infrared (IR) spectra were recorded on an Agilent Technologies Cary 630 FT-IR spectrometer equipped with an ATR unit and the signals are reported in wavenumbers (cm 1 ). lting points (m.p.) were determined with a Stuart Scientific SMP20 melting point apparatus and are not corrected. Mass spectra (MS) were obtained from the Analytical Facility at the Institut für Chemie, Technische Universität Berlin. S1

2 2. The detection of stabilized silylium ion In a glove box, a flame-dried 1-mL tube is charged with [H(OEt 2 ) 2 ] + [BAr F 4] (40.5 mg, 0.04 mmol) and C 6 D 6 (0.10 ml). Then hydrosilane 1a (6.1 µl, 0.04 mmol) was added using micro syringe. A lot of bubbles were generated right away. After 10 min, no more bubbles were released and a biphasic mixture was formed. C 6 D 6 (0.15 ml 3) was then added into the tube, and the top phase was carefully removed with pipette. The remaining liquid was transferred into an MR tube using 1,2-Cl 2 C 6 D 4. By recording a 1 H- 29 Si HMQC spectrum at room temperature, this sample showed a characteristic signal at δ = 53.2 ppm. 3. Typical procedures for C H silylation thod A: In a glove box, [H(OEt 2 ) 2 ] + [BAr F 4] (2.0 mg, mmol) and norbornene (18.8 mg, 0.20 mmol) are added to a 2-mL GLC-vial equipped with a stirring bar, followed by the addition of the hydrosilane (0.20 mmol) and the heteroarene (0.40 mmol). After sealing the vial with cap, the reaction is performed in an open-vessel mode allowing perforation of the cap with a cannula (0.9 mm thickness) to liberate the formed dihydrogen gas (for reactions at 80 o C, no perforation of the cap is made). After 18 h at indicated temperature, the reaction mixture is quenched with Et 3 (0.1 ml) and directly subjected to flash column chromatography on silica gel (3 cm silica gel) using cyclohexane/tert-butyl methyl ether/et 3 (90/4/10) mixtures. The thus obtained silylated indoles contain unreacted and reduced heteroarene, which are removed under high vacuum (0.5 mbar) at elevated temperatures ( o C), affording the analytically pure silylated products. The regioselectivity is verified by GLC analysis and 1 H MR spectroscopy prior to purification. o norbornane and silylated norbornane detected by GLC-MS analysis. thod B: In a glove box, [H(OEt 2 ) 2 ] + [BAr F 4] (2.0 mg, mmol) and norbornene (18.8 mg, 0.20 mmol) are added to a 2-mL GLC-vial equipped with a stirring bar, followed by the addition of the hydrosilane (0.20 mmol) and indole 4a (0.60 mmol). After sealing the vial with a cap, the reaction is performed in an open-vessel mode allowing perforation of the cap with a cannula (0.9 mm thickness) to liberate the formed dihydrogen gas. After 18 h at room temperature, a lot of precipitate is generated. The precipitate is filtered off, and the obtained solid is washed with cyclohexane (1 ml 3) to afford the analytically pure silylated products. The regioselectivity was verified by GLC analysis and 1 H MR spectroscopy prior to purification. o norbornane and silylated norbornane detected by GLC-MS analysis. thod C: In a glove box, [H(OEt 2 ) 2 ] + [BAr F 4] (2.0 mg, mmol) and norbornene (18.8 mg, 0.20 mmol) are added to a 2-mL GLC-vial equipped with a stirring bar, followed by the addition of the hydrosilane (0.40 mmol) and the electron-rich arene (0.20 mmol). After sealing the vial with a cap, the reactions are performed in an open-vessel mode allowing perforation of the cap with a cannula (0.9 mm thickness) to liberate the formed dihydrogen gas (for reactions at 80 o C, no perforation of the cap is made). After 18 h at indicated temperature, the reaction mixture is quenched with Et 3 (0.1 ml) and directly subjected to flash column chromatography on silica gel using cyclohexane/et 3 mixtures (96/4). The thus-obtained silylated product may contain unreacted starting material, which is removed under high vacuum (0.5 mbar) at elevated S2

3 temperatures (60-80 o C), affording the analytically pure silylated products. The regioselectivity is verified by GLC analysis and 1 H MR spectroscopy prior to purification. o norbornane and silylated norbornane detected by GLC-MS analysis. 4. Gram-scale synthesis of C-3 silylated indole In a glove box, [H(OEt 2 ) 2 ] + [BAr F 4] (25.3 mg, mmol) and norbornene (471 mg, 5.0 mmol) were added to a flame-dried 20-mL Schlenk tube equipped with a stirring bar, followed by the addition of hydrosilane 1b (992 mg, 5.0 mmol) and indole 4a (1.312 g, 10.0 mmol). After sealing the tube with a rubber septum, the reaction was performed in an open-vessel mode allowing perforation of the cap with a cannula (0.9 mm thickness) to liberate the formed dihydrogen gas. After 18h at room temperature, the reaction mixture was quenched with Et 3 (0.5 ml) and directly subjected to flash column chromatography on silica gel (3 cm silica gel) using cyclohexane/tert-butyl methyl ether/et 3 mixtures (90/4/10). The thus-obtained silylated indoles contained unreacted and reduced indole, which were removed under high vacuum (0.5 mbar) at elevated temperatures (120 o C) to afford the analytically pure title compound 5ab as a pale yellow oil (1.56 g, 95% yield). 5. Characterization data SiPh 2 1-thyl-3-dimethylphenylsilylindole (5aa): (thod A at 80 o C) colorless oil, 96% yield. 1 H MR (500 MHz, CDCl 3 ) δ (m, 3H), (m, 4H), (m, 1H), (m, 1H), 7.09 (s, 1H), 3.82 (s, 3H), 0.69 (s, 6H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ 139.6, 138.7, 136.5, 134.2, 133.0, 129.0, 127.9, 122.2, 121.7, 119.6, 109.5, 107.1, 32.9, -1.2 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 1504, 1460, 1420, 1328, 1300, 1246, 1185, 1107, 1046, 973, 807, 774, 728 cm -1. SiPh 2 1-thyl-3-methyldiphenylsilylindole (5ab): (thod A at rt) colorless oil, 93% yield. 1 H MR (500 MHz, CDCl 3 ) δ (m, 4H), (m, 1H), (m, 7H), (m, 1H), (m, 1H), (m, 1H), 3.82 (s, 3H), 1.00 (s, 3H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ 138.8, 138.0, 137.5, 135.2, 133.2, 129.3, 127.9, 122.5, 121.8, 119.7, 109.5, 105.1, 32.9, -2.2 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 1503, 1460, 1427, 1328, 1240, 1183, 1105, 1046, 972, 908, 784, 719 cm thyl-3-diphenylsilanylindole (5af): (thod A at rt) colorless oil, 96% yield. 1 H MR (500 MHz, CDCl 3 ) δ (m, 4H), 7.61 (dd, J = 7.9, 0.8 Hz, 1H), (m, 7H), (m, 1H), (m, 2H), 5.76 (d, J = 1.1 Hz, 1H), 3.82 (s, 3H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ 138.6, 138.4, S3

4 135.8, 134.6, 133.3, 129.7, 128.1, 122.1, 122.0, 120.0, 109.6, 102.0, 33.0 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 2111, 1504, 1460, 1421, 1328, 1302, 1241, 1187, 1104, 975, 794, 721 cm -1. HRMS (EI) calculated for C 21 H 19 Si [M] , found Ph 3,3'-(thylphenylsilanediyl)bis(1-methyl-1H-indole) (7ag): (thod B, Si at rt) white solid, m.p. = 156 C (cyclohexane), 73% yield. 1 H MR (500 MHz, CDCl 3 ) δ 7.72 (d, J = 7.6 Hz, 2H), 7.60 (d, J = 7.9 Hz, 2H), (m, 5H), 7.27 (t, J = 7.6 Hz, 2H), (m, 4H), 3.79 (s, 6H), 0.98 (s, 3H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ 138.8, 138.6, 137.9, 135.1, 133.3, 129.1, 127.9, 122.6, 121.6, 119.5, 109.4, 106.3, 32.9, -1.1 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 1501, 1459, 1421, 1327, 1239, 1183, 1104, 1012, 976, 780, 734 cm -1. HRMS (EI) calculated for C 25 H 24 2 Si [M] , found SiEt 2 H 1-thyl-3-diethylsilanylindole (5ah): (thod A at rt, indole 4a (0.20 mmol), Et 2 SiH 2 (0.40 mmol)) pale yellow oil, 61% yield. 1 H MR (500 MHz, CDCl 3 ) δ (m, 1H), 7.36 (d, J = 8.2 Hz, 1H), (m, 1H), (m, 2H), 4.44 (p, J = 3.3 Hz, 1H), 3.82 (s, 3H), (m, 6H), (m, 4H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ 138.4, 136.4, 133.5, 121.9, 121.8, 119.6, , 103.9, 32.9, 8.6, 4.4 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 2094, 1504, 1460, 1419, 1327, 1240, 1187, 1012, 979, 799, 736 cm -1. HRMS (EI) calculated for C 13 H 19 Si [M] , found Ph H 3,3'-(Phenylsilanediyl)bis(1-methyl-1H-indole) (7ai): (thod B, at rt) Si white solid, m.p. = 144 C (cyclohexane), 74% yield. 1 H MR (500 MHz, d 6 -acetone) δ (m, 2H), (m, 2H), 7.43 (d, J = 8.2 Hz, 2H), (m, 3H), 7.32 (s, 2H), (m, 2H), (m, 2H), 5.81 (s, 1H), 3.85 (s, 6H) ppm. 13 C MR (126 MHz, d 6 -acetone) δ 139.7, 139.0, 136.8, 136.1, 134.3, 130.2, 128.7, 122.4, 120.3, 110.5, 103.0, 33.0 ppm. 29 Si MR (99 MHz, d 6 -acetone) δ ppm. IR (ATR): 2100, 1502, 1459, 1419, 1327, 1241, 1181, 977, 789, 734 cm -1. HRMS (EI) calculated for C 24 H 22 2 Si [M] , found SiPh 1,2-Dimethyl-3-diphenylsilanylindole (5bf): (thod A at 40 o 2 H C) colorless oil, 93% yield. 1 H MR (500 MHz, CDCl 3 ) δ (m, 4H), (m, 7H), 7.35 (d, J = 8.2 Hz, 1H), (m, 1H), (m, 1H), 5.84 (s, 1H), 3.74 (s, 3H), 2.48 (s, 3H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ 145.5, 138.5, 135.9, 134.6, 133.3, 129.6, 128.1, 121.2, 120.9, 119.8, 109.0, 98.3, 29.8, 13.4 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 2113, 1507, 1466, 1426, 1391, 1331, 1103, 1026, 889, 796, 730 cm -1. HRMS (EI) calculated for C 22 H 21 Si [M] , found ,5-Dimethyl-3-diphenylsilanylindole (5df): (thod A at rt) colorless oil, 94% yield. 1 H MR (500 MHz, CDCl 3 ) δ (m, 4H), (m, 7H), 7.32 (d, J = 8.3 Hz, 1H), 7.17 (dd, J = 8.3, 1.5 Hz, 1H), 7.11 (s, 1H), 5.76 (s, 1H), 3.80 (s, 3H), 2.47 (s, 3H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ 138.4, 137.0, 135.8, 134.7, 133.7, 129.6, 129.2, 128.1, 123.6, 121.8, 109.2, 101.2, 33.0, S4

5 21.6 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 2111, 1504, 1421, 1356, 1326, 1243, 1197, 1147, 1106, 1046, 861, 189, 729 cm -1. HRMS (EI) calculated for C 22 H 21 Si [M] , found thyl-3-diphenylsilanyl-5-fluoroindole (5ef): (thod A at rt) colorless F oil, 98% yield. 1 H MR (500 MHz, CDCl 3 ) δ 7.71 (dd, J = 7.9, 1.4 Hz, 4H), (m, 6H), 7.28 (dd, J = 8.9, 4.3 Hz, 1H), (m, 2H), 7.04 (td, J = 9.0, 2.4 Hz, 1H), 5.69 (s, 1H), 3.79 (s, 3H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ (d, J = Hz), 139.7, 135.7, 135.3, 134.2, (d, J = 10.2 Hz), 129.8, 128.2, (d, J = 26.5 Hz), (d, J = 9.7 Hz), (d, J = 23.1 Hz), (d, J = 4.7 Hz), 33.3 ppm. 19 F MR (471 MHz, CDCl 3 ) δ ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 2119, 1504, 1478, 1428, 1332, 1192, 1162, 1112, 987, 905, 877, 791, 726 cm -1. HRMS (EI) calculated for C 21 H 18 FSi [M] , found thyl-3-diphenylsilanyl-5-chloroindole (5ff): (thod A at rt) colorless Cl oil, 96% yield. 1 H MR (500 MHz, CDCl 3 ) δ (m, 4H), (m, 1H), (m, 6H), (m, 2H), 7.16 (s, 1H), 5.73 (s, 1H), 3.79 (s, 3H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ 139.5, 137.1, 135.7, 134.4, 134.0, 129.9, 128.2, 125.8, 122.4, 121.4, 110.6, 102.0, 33.2 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 2103, 1503, 1467, 1421, 1329, 1241, 1183, 1104, 977, 870, 786, 725 cm -1. HRMS (EI) calculated for C 21 H 18 ClSi [M] , found thyl-3-diphenylsilanyl-5-bromoindole (5gf): (thod A at rt) white Br solid, m.p. = 126 C (cyclohexane), 96% yield. 1 H MR (500 MHz, CDCl 3 ) δ (m, 5H), (m, 7H), 7.23 (d, J = 8.6 Hz, 1H), 7.10 (s, 1H), 5.68 (s, 1H), 3.76 (s, 3H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ 139.3, 137.4, 135.7, 135.1, 134.0, 129.9, 128.2, 125.0, 124.5, 113.5, 111.0, 102.1, 33.2 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 2099, 1501, 1465, 1427, 1419, 1327, 1240, 1188, 1103, 973, 870, 796, 782, 725 cm -1. HRMS (EI) calculated for C 21 H 18 BrSi [M] , found thyl-3-diphenylsilanyl-6-fluoroindole (5hf): (thod A at rt), colorless F oil, 89% yield; along with <10% of 1-methyl-3-diphenylsilanyl-6-fluoroindoline. H MR (500 MHz, CDCl 3 ) δ (m, 4H), (m, 8H), 7.11 (s, 1H), 7.06 (dd, J = 9.6, 2.3 Hz, 1H), (m, 1H), 5.69 (s, 1H), 3.75 (s, 3H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ (d, J = Hz), (d, J = 3.5 Hz), 135.7, 135.5, 134.3, 129.8, 129.6, 128.2, (d, J = 10.2 Hz), (d, J = 24.4 Hz), 102.5, 96.1 (d, J = 26.2 Hz), 33.1 ppm. 19 F MR (471 MHz, CDCl 3 ) δ ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 2123, 1507, 1466, 1428, 1328, 1241, 1173, 1110, 1092, 906, 894, 802, 727 cm -1. HRMS (EI) calculated for C 21 H 18 FSi [M] , found (Diphenylsilanyl)-,-dimethylaniline (9af): (thod C at rt) colorless oil, 67% yield. 1 H MR (500 MHz, CDCl 3 ) δ 7.61 (dd, J = 7.9, 1.5 Hz, 4H), (m, 8H), 6.76 (d, J = 8.7 Hz, 2H), 5.47 (s, 1H), 2.99 (s, 6H) S5

6 ppm. 13 C MR (126 MHz, CDCl 3 ) δ 151.6, 137.1, 135.9, 134.7, 129.6, 128.1, 117.8, 112.1, 40.2 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 2109, 1594, 1511, 1427, 1354, 1227, 1205, 1111, 794, 729 cm (4-Diphenylsilanyl-phenyl)-pyrrolidine (9bf): (thod C at 80 o C) colorless oil, 66% yield, 1 H MR (500 MHz, CDCl 3 ) δ (m, 4H), (m, 8H), 6.63 (d, J = 8.6 Hz, 2H), 5.50 (s, 1H), 3.34 (t, J = 6.6 Hz, 4H), (m, 4H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ 149.0, 137.2, 135.9, 134.9, 129.6, 128.0, 116.5, 111.7, 47.5, 25.6 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 2108, 1594, 1510, 1484, 1427, 1375, 1119, 1112, 793, 729 cm -1. SiPh 5-(Diphenylsilanyl)-1-methylindoline (9cf): (thod C at 80 o 2 H C) colorless oil, 70% yield. 1 H MR (500 MHz, CDCl 3 ) δ 7.65 (dd, J = 7.8, 1.5 Hz, 4H), (m, 6H), (m, 1H), 7.30 (s, 1H), 6.53 (d, J = 7.8 Hz, 1H), 5.48 (s, 1H), 3.38 (t, J = 8.3 Hz, 2H), 2.98 (t, J = 8.2 Hz, 2H), 2.82 (s, 3H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ 155.0, 136.1, 135.9, 134.7, 131.3, 130.3, 129.6, 128.0, 119.4, 106.8, 55.7, 35.6, 28.6 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 2109, 1600, 1494, 1427, 1375, 1289, 1260, 1170, 1110, 1067, 888, 791, 727 cm -1. HRMS (APCI) calculated for C 21 H 22 Si [M+H] , found (Diphenylsilanyl)-1-methyl-1,2,3,4-tetrahydroquinoline (9df): (thod C at 80 o C) colorless oil, 73% yield. 1 H MR (500 MHz, CDCl 3 ) δ (m, 4H), (m, 6H), 7.32 (dd, J = 8.1, 1.5 Hz, 1H), 7.19 (d, J = 1.1 Hz, 1H), 6.64 (d, J = 8.1 Hz, 1H), (m, 1H), 3.30 (t, J = 5.6 Hz, 2H), 2.94 (s, 3H), 2.77 (t, J = 6.2 Hz, 2H), (m, 2H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ 148.0, 136.3, 135.9, 135.3, 134.8, 129.6, 128.0, 122.4, 117.3, 110.5, 51.3, 38.8, 27.9, 22.3 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 2109, 1594, 1509, 1427, 1388, 1320, 1205, 1109, 1088, 999, 855, 790, 727 cm thyl-4-(diphenylsilanyl)-,-dimethylaniline (9ef): (thod C at rt) colorless oil, 63% yield. 1 H MR (500 MHz, CDCl 3 ) δ 7.59 (dd, J = 7.8, 1.4 Hz, 4H), (m, 6H), 7.22 (d, J = 8.3 Hz, 1H), 6.62 (d, J = 2.2 Hz, 1H), 6.55 (dd, J = 8.3, 2.4 Hz, 1H), 5.57 (s, 1H), 2.99 (s, 6H), 2.35 (s, 3H) ppm. 13 C MR (126 MHz, CDCl 3 ) δ 152.1, 146.0, 138.4, 136.0, 134.6, 129.5, 128.0, 117.1, 113.8, 109.2, 40.2, 23.5 ppm. 29 Si MR (99 MHz, CDCl 3 ) δ ppm. IR (ATR): 2111, 1593, 1542, 1498, 1427, 1355, 1209, 1106, 1059, 791, 731 cm Molecular structure and X-ray data of compound 7ai Data for the single-crystal structure determination were collected with an Agilent Superova diffractometer equipped with a CCD area Atlas detector and a mirror monochromator by utilizing Cu-Kα radiation (λ = Å). Software packages used: CrysAlis PRO for data collection, cell refinement, and data reduction, 2 SHELXS-97 for structure solution, 3 SHELXL-97 for structure refinement, 4 and CYLview 5 for graphics. S6

7 Crystal data and structure refinement for 7ai: Identification code Empirical formula cu-1827 C24 H22 2 Si Formula weight Temperature Wavelength Crystal system (10) K Å Triclinic Space group P-1 Unit cell dimensions a = (3) Å a= (3). b = (4) Å b= (3). c = (7) Å g = (3). Volume (11) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 776 Crystal size 0.31 x 0.26 x 0.11 mm 3 Theta range for data collection 4.15 to Index ranges -9<=h<=10, -13<=k<=13, -24<=l<=24 S7

8 Reflections collected Independent reflections 7232 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 7232 / 0 / 497 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å References 1) Brookhart, M.; Grant, B.; Volpe, A. F., Jr. Organometallics 1992, 11, ) Agilent CrysAlis PRO, 2012, Agilent Technologies, Yarnton, UK. 3) Sheldrick, G. M. Acta Crystallogr. Sect. A. 1990, 46, ) Sheldrick, G. M. Acta Crystallogr. Sect. A. 2008, 64, ) CYLview, 1.0b; Legault, C. Y., Université de Sherbrooke, 2009 ( S8

9 8. Copy of MR spectra 1 H MR (500 MHz, 1,2-Cl 2 C 6 D 4 ) of 3a: 1 H, 29 Si HMQC (500 MHz, 1,2-Cl 2 C 6 D 4 ) of 3a: S9

10 1 H MR (500 MHz, CDCl 3 ) of 5aa: 13 C MR (126 MHz, CDCl 3 ) of 5aa: S10

11 29 Si MR (99 MHz, CDCl 3 ) of 5aa: 1 H MR (500 MHz, CDCl 3 ) of 5ab: S11

12 13 C MR (126 MHz, CDCl 3 ) of 5ab: 29 Si MR (99 MHz, CDCl 3 ) of 5ab: S12

13 1 H MR (500 MHz, CDCl 3 ) of 5af: 13 C MR (126 MHz, CDCl 3 ) of 5af: S13

14 29 Si MR (99 MHz, CDCl 3 ) of 5af: 1 H MR (500 MHz, CDCl 3 ) of 7ag: Ph Si S14

15 13 C MR (126 MHz, CDCl 3 ) of 7ag: Ph Si 29 Si MR (99 MHz, CDCl 3 ) of 7ag: Ph Si S15

16 1 H MR (500 MHz, CDCl 3 ) of 5ah: SiEt 2 H 13 C MR (126 MHz, CDCl 3 ) of 5ah: SiEt 2 H S16

17 29 Si MR (99 MHz, CDCl 3 ) of 5ah: SiEt 2 H 1 H MR (500 MHz, d 6 -acetone) of 7ai: Ph H Si S17

18 13 C MR (126 MHz, d 6 -acetone) of 7ai: Ph H Si 29 Si MR (99 MHz, d 6 -acetone) of 7ai: Ph H Si S18

19 1 H MR (500 MHz, CDCl 3 ) of 5bf: 13 C MR (126 MHz, CDCl 3 ) of 5bf: S19

20 29 Si MR (99 MHz, CDCl 3 ) of 5bf: 1 H MR (500 MHz, CDCl 3 ) of 5df: S20

21 13 C MR (126 MHz, CDCl 3 ) of 5df: 29 Si MR (99 MHz, CDCl 3 ) of 5df: S21

22 1 H MR (500 MHz, CDCl 3 ) of 5ef: 13 C MR (126 MHz, CDCl 3 ) of 5ef: S22

23 19 F MR (471 MHz, CDCl 3 ) of 5ef: 29 Si MR (99 MHz, CDCl 3 ) of 5ef: S23

24 1 H MR (500 MHz, CDCl 3 ) of 5ff: 13 C MR (126 MHz, CDCl 3 ) of 5ff: S24

25 29 Si MR (99 MHz, CDCl 3 ) of 5ff: 1 H MR (500 MHz, CDCl 3 ) of 5gf: S25

26 13 C MR (126 MHz, CDCl 3 ) of 5gf: 29 Si MR (99 MHz, CDCl 3 ) of 5gf: S26

27 1 H MR (500 MHz, CDCl 3 ) of 5hf: 13 C MR (126 MHz, CDCl 3 ) of 5hf: S27

28 19 F MR (471 MHz, CDCl 3 ) of 5hf: 29 Si MR (99 MHz, CDCl 3 ) of 5hf: S28

29 1 H MR (500 MHz, CDCl 3 ) of 9af: 2 13 C MR (126 MHz, CDCl 3 ) of 9af: 2 S29

30 29 Si MR (99 MHz, CDCl 3 ) of 9af: 2 1 H MR (500 MHz, CDCl 3 ) of 9bf: S30

31 13 C MR (126 MHz, CDCl 3 ) of 9bf: 29 Si MR (99 MHz, CDCl 3 ) of 9bf: S31

32 1 H MR (500 MHz, CDCl 3 ) of 9cf: 13 C MR (126 MHz, CDCl 3 ) of 9cf: S32

33 29 Si MR (99 MHz, CDCl 3 ) of 9cf: 1 H MR (500 MHz, CDCl 3 ) of 9df: S33

34 13 C MR (126 MHz, CDCl 3 ) of 9df: 29 Si MR (99 MHz, CDCl 3 ) of 9df: S34

35 1 H MR (500 MHz, CDCl 3 ) of 9ef: 2 13 C MR (126 MHz, CDCl 3 ) of 9ef: 2 S35

36 29 Si MR (99 MHz, CDCl 3 ) of 9ef: 2 S36