S1 Supporting Information for the Paper AgNO3·SiO2: Convenient AgNPs Source for the Sustainable Hydrofunctionalization of Allenyl-Indoles using Heterogeneous Catalysis Amparo Luna,*,† Fernando Herrera,† Sheila Higuera,† Alejandro Murillo,† Israel Fernández,§ and Pedro Almendros*,‡ †Grupo de Lactamas y Heterociclos Bioactivos, Departamento de Química Orgánica, Unidad Asociada al CSIC, Facultad de Química, Universidad Complutense de Madrid, 28040-Madrid, Spain §Departamento de Química Orgánica and Centro de Innovación en Química Avanzada (ORFEO- CINQA), Facultad de Química, Universidad Complutense de Madrid, 28040-Madrid, Spain ‡Instituto de Química Orgánica General, IQOG, CSIC, Juan de la Cierva 3, 28006-Madrid, Spain E-mail: alunac@quim.ucm.es; palmendros@iqog.csic.es Table of Contents General Methods S2 Experimental Procedures S2–S18 Electron Microscopy Study S18–S19 Raman Study S20 1H NMR, 13C NMR, and 19F NMR Spectra S21–S62 Computational Details and Cartesian Coordinates S63–S72 S2 General Methods: 1H NMR, 13C NMR, and 19F NMR spectra were recorded on a Bruker Avance AMX-700, Bruker AMX-500, or Bruker Avance-DPX 300. NMR spectra were recorded in CDCl3, CD3CN or C6D6, solutions, except otherwise stated. Chemical shifts are given in ppm relative to TMS (1H, 0.0 ppm), CDCl3 (1H, 7.27 ppm; 13C, 76.9 ppm), CD3CN (1H, 1.94 ppm; 13C, 118.3 ppm) and C6D6 (1H, 7.16 ppm; 13C, 128.0 ppm). Low- and high-resolution mass spectra were taken on an AGILENT 6520 Accurate Mass QTOF LC/MS spectrometer using the electronic impact (EI) or electrospray modes (ES) unless otherwise stated. IR spectra were recorded on a Bruker Tensor 27 spectrometer. Dispersive Raman spectra at 532 nm were recorded in a RM 1000 Renishaw Invia Raman Microscope System. The Raman spectrometer is equipped with a Leica microscope and an electrically refrigerated CCD camera. The spectra were obtained with ×50 magnification objective lenses. The final spectra were the result of 10 accumulations to improve the signal-to-noise ratio and the integration time was 10 s. The software employed for data acquisition and analysis was Wire for Windows and Galactic Industries GRAMS/32TM. Five scans were recorded to improve the signal- to-noise ratio. The Raman shift was calibrated before the measurements according to the silicon peak at 520 cm−1. The 532 nm line had a laser power from 0.0005 to 5 mW. The measurements were done directly in the sample (in situ), the sample preparation is not necessary. All commercially available compounds were used without further purification. General procedure for the preparation of allenes 1a–h. The corresponding indole (1.054 g, 9 mmol) was added to a stirred solution of the appropriate α-allenol (1 mmol) in dichloroethane (12 mL) under argon atmosphere. Then, TsOH⋅H2O (57 mg, 0.3 mmol) was added at room temperature. After disappearance of the starting material (TLC), the reaction mixture was filtered through a short column of silica gel (ethyl ether, 2 x 10 mL). Chromatography of the residue using hexanes/ethyl acetate or toluene/ethyl acetate mixtures gave analytically pure compounds. Spectroscopic and analytical data for previously unreported allenes follow. S3 Allene-1a. From 381 mg (2 mmol) of the corresponding α-allenic alcohol, and after chromatography of the residue using hexanes/ethyl acetate (98:2) as eluent, gave compound 1a (359 mg, 62%) as a pale brown solid; mp 92–94 ºC; 1H NMR (300 MHz, CDCl3, 25 oC) : 7.94 (br s, 1H), 7.51 (d, J = 7.9 Hz, 1H), 7.35 (d, J = 8.1 Hz, 1H), 7.26 (m, 2H), 7.18 (m, 1H), 7.07 (td, J = 7.5, 7.1, 1.0 Hz, 1H), 6.85 (d, J = 8.7 Hz, 2H), 6.81 (dd, J = 2.4, 0.8 Hz, 1H), 4.78 (s, 1H), 4.51 (m, 2H), 3.81 (s, 3H), 1.79 (t, J = 3.1 Hz, 3H); 13C NMR (75 MHz, CDCl3, 25 oC) : 207.5, 158.0, 136.4, 134.7, 129.6 (2C), 127.2, 122.9, 121.8, 119.7, 119.2, 118.4, 113.4 (2C), 111.0, 101.9, 75.4, 55.2, 46.6, 18.4; IR (CHCl3, cm–1):  3412, 1957. Allene-1b. From 230 mg (0.91 mmol) of the corresponding α-allenic alcohol, and after chromatography of the residue using hexanes/ethyl acetate (6:1) as eluent, gave compound 1b (147 mg, 47%) as a yellow oil; 1H NMR (300 MHz, CDCl3, 25 oC) : 7.88 (br s, 1H), 7.49 (m, 3H), 7.33 (m, 1H), 7.27 (m, 4H), 7.48 (m, 2H), 7.06 (ddd, J = 8.0, 7.1, 1.0 Hz, 1H), 6.84 (d, J = 8.7 Hz, 2H), 6.73 (dd, J = 2.4, 0.9 Hz, 1H), 5.43 (s, 1H), 4.85(m, 2H), 3.79 (s, 3H); 13C NMR (75 MHz, CDCl3, 25 oC) : 210.3, 158.0 (2C), 136.6, 136.3, 134.7, 129.7 (2C), 128.3 (2C), 127.0, 126.5 (2C), 123.6, 121.9, 119.6, 119.3, 119.0, 113.4 (2C), 111.0, 109.3, 79.8, 55.1, 42.9; IR (CHCl3, cm–1):  3421, 1936. S4 Allene-1c. From 380 mg (2 mmol) of the corresponding α-allenic alcohol, and after chromatography of the residue using hexanes/ethyl acetate (98:2) as eluent, gave compound 1c (348 mg, 56%) as a pale brown solid; mp 85–87 ºC; 1H NMR (300 MHz, CDCl3, 25 oC) : 7.87 (br s, 1H), 7.28–7.23 (m, 4H), 7.01 (dd, J = 8.3, 1.3 Hz, 1H), 6.85 (d, J = 8.8 Hz, 2H), 6.78 (m, 1H), 4.74 (s, 1H), 4.50 (m, 2H), 3.81 (s, 3H), 2.43 (s, 3H), 1.79 (t, J = 3.1 Hz, 3H); 13C NMR (75 MHz, CDCl3, 25 oC) : 207.6, 158.0, 134.8, 129.6 (2C), 128.4, 123.5, 123.0, 119.3, 118.0, 117.4, 117.2, 113.4 (2C), 110.6, 102.0, 75.3, 55.2, 46.5, 21.6, 18.4; IR (CHCl3, cm–1):  3409, 1957. Allene-1d. From 287 mg (1.5 mmol) of the corresponding α-allenic alcohol, and after chromatography of the residue using hexanes/ethyl acetate (10:1) as eluent, gave compound 1d (195 mg, 41%) as a pale yellow oil; 1H NMR (300 MHz, CDCl3, 25 oC) : 7.88 (s, 1H), 7.26 (m, 3H), 6.98 (d, J = 2.3 Hz, 1H), 6.88 (d, J = 8.7 Hz, 3H), 6.82 (d, J = 2.1 Hz, 1H), 4.75 (s, 1H), 4.55 (m, 2H), 3.84 (s, 3H), 3.83 (s, 3H), 1.81 (t, J = 3.0 Hz, 3H); 13C NMR (75 MHz, CDCl3, 25 oC) : 207.6, 158.0, 153.7, 134.6, 131.7, 129.6 (2C), 127.7, 123.8, 118.1, 113.4 (2C), 111.8, 111.6, 101.9, 101.8, 75.3, 55.9, 55.2, 46.6, 18.3; IR (CHCl3, cm–1):  3417, 1957. S5 Allene-1e. From 380 mg (2 mmol) of the corresponding α-allenic alcohol, and after chromatography of the residue using hexanes/ethyl acetate (98:2) as eluent, gave compound 1e (248 mg, 35%) as a yellow oil; 1H NMR (300 MHz, CDCl3, 25 oC) : 7.97 (s, 1H), 7.64 (m, 1H), 7.24 (m, 4H), 6.86 (d, J = 8.8 Hz, 2H), 6.77 (m, 1H), 4.68 (s, 1H), 4.49 (m, 2H), 3.82 (s, 3H), 1.77 (t, J = 3.1 Hz, 3H); 13C NMR (75 MHz, CDCl3, 25 oC) : 207.5, 164.3, 158.2, 135.1, 134.1, 129.5 (2C), 124.8, 124.1, 122.3, 118.6 (2C), 113.6, 112.6, 112.4, 101.7, 75.7, 55.2, 46.4, 18.4; IR (CHCl3, cm–1):  3414, 1957. Allene-1f. From 190 mg (1 mmol) of the corresponding α-allenic alcohol, and after chromatography of the residue using hexanes/ethyl acetate (13:1) as eluent, gave compound 1f (159 mg, 52%) as a colorless oil; 1H NMR (300 MHz, CDCl3, 25 oC) : 7.98 (s, 1H), 7.30 (d, J = 8.8 Hz, 2H), 7.28 (m, 1H), 7.20 (dd, J = 9.8, 2.4 Hz, 1H), 6.99 (dd, J = 9.0, 2.6 Hz, 1H), 6.92 (d, J = 8.7 Hz, 2H), 6.88 (m, 1H), 4.74 (s, 1H), 4.57 (m, 2H), 3.87 (s, 3H), 1.84 (t, J = 3.0 Hz, 3H); 13C NMR (75 MHz, CDCl3, 25 oC) : 207.5, 158.2, 157.6 (d, J = 232.6 Hz), 134.2, 132.9, 129.5 (2C), 127.6 (d, J = 9.9 Hz), 124.6, 118.4 (d, J = 4.5 Hz), 113.5 (2C), 111.5 (d, J = 9.7 Hz), 110.2 (d, J = 26.3 Hz), 104.7 (d, J = 23.3 Hz), 101.6, 75.5, 55.2, 46.6, 18.3; 19F NMR (282 MHz, CDCl3, 25 °C): δ = −124.8 (s, 1F); IR (CHCl3, cm–1):  3426, 1957. S6 Allene-1g. From 200 mg (0.80 mmol) of the corresponding α-allenic alcohol, and after chromatography of the residue using toluene/ethyl acetate (15:1) as eluent, gave compound 1a (132 mg, 47%) as a yellow oil; 1H NMR (300 MHz, CDCl3, 25 oC) : 8.02 (s, 1H), 7.55 (d, J = 7.9 Hz, 1H), 7.36 (d, J = 8.1 Hz, 1H), 7.19 (m, 1H), 7.10 (m, 1H), 6.82 (d, J = 1.6 Hz, 1H), 6.61 (s, 2H), 4.76 (s, 1H), 4.53 (m, 2H), 3.86 (s, 3H), 3.81 (s, 6H), 1.81 (t, J = 3.0 Hz, 3H); 13C NMR (75 MHz, CDCl3, 25 oC) : 207.6, 152.9 (2C), 138.2, 136.5, 136.4, 127.2, 122.9, 121.9, 119.7, 119.3, 118.2, 111.0, 105.8 (2C), 101.6, 75.5, 60.8, 56.1 (2C), 47.8, 18.4; IR (CHCl3, cm–1):  3414, 1956. Allene-1h. From 200 mg (0.98 mmol) of the corresponding α-allenic alcohol, and after chromatography of the residue using hexanes/ethyl acetate (9:1) as eluent, gave compound 1h (103 mg, 35%) as a yellow oil; 1H NMR (300 MHz, CDCl3, 25 oC) : 7.98 (s, 1H), 7.50 (d, J = 7.9 Hz, 1H), 7.35 (dt, J = 8.2, 0.9 Hz, 1H), 7.18 (m, 1H), 7.08 (m, 1H), 6.85 (m, 2H), 6.76 (m, 2H), 5.94 (m, 2H), 4.73 (m, 1H), 4.52 (m, 2H), 1.80 (t, J = 3.1 Hz, 3H); 13C NMR (75 MHz, CDCl3, 25 oC) : 207.7, 147.5, 146.1, 136.8, 136.6, 127.4, 123.0, 122.1, 121.8, 119.8, 119.4, 118.4, 111.2, 109.3, 107.9, 101.9, 100.9, 75.7, 47.3, 18.6; IR (CHCl3, cm–1):  3412, 1954. General procedure for the preparation of AgNPs. 1 weight% AgNO3•SiO2 was prepared by adding AgNO3 (100 mg) to a slurry of Scharlau silica gel 60 (9.90 g, 0.04-0.06 mm, 230-400 mesh) in deionized water (27 ml). The mixture was stirred for 15 minutes, concentrated under vacuum at 60 S7 ºC to form a free-flowing powder and dried by heating to 140 ºC under high vacuum for 6-7 hours. Nanoparticles were kept in the dark at room temperature under argon atmosphere and can be stored for 1.5-month period. General procedure for the AgNPs-catalyzed preparation of carbazoles 2a–2h. To a solution of the appropriate allene 1 (0.15 mmol) in dichloroethane (1.4 ml) was added 1 weight% AgNO3•SiO2. The sealed tube containing the solution was heated in the dark at 150 ºC until the starting material disappeared, as indicated by TLC. The crude reaction was filtered with vacuum filtration and the residue was washed with dichloroethane (3 x 2 ml). The solution was transferred into a 25 mL round- bottom flask using dichloromethane. After removal of the solvent in vacuum, the residue was purified by column chromatography on silica gel to give analytically pure compounds. Spectroscopic and analytical data for products 2a–2h follow. Carbazole 2a. From 30 mg (0.10 mmol) of allene 1a, and after chromatography of the residue using hexanes/ethyl acetate (9:1) as eluent, gave compound 2a (24 mg, 84%) as a yellow solid; mp 142144 ºC; 1H NMR (300 MHz, CDCl3, 25 ºC) δ: 8.07 (m, 1H), 7.95 (d, J = 8.0 Hz, 1H), 7.77 (br s, 1H), 7.38 (d, J = 8.8 Hz, 2H), 7.33 (m, 2H), 7.23 (m, 1H), 7.19 (d, J = 7.8 Hz, 1H), 7.10 (d, J = 8.7 Hz, 2H), 3.92 (s, 3H), 2.37 (s, 3H); 13C NMR (75 MHz, CDCl3, 25 ºC) δ: 159.0, 139.4, 139.0, 133.3, 130.9 (2C), 129.6, 125.3, 124.0, 123.7, 121.9, 121.0, 120.1, 119.3, 118.8, 114.4 (2C), 110.5, 55.4, 20.1; IR (CH2Cl2, cm-1) ν: 3379; HRMS (ES): calcd for C20H18NO [M + H]+: 288.1383; found: 288.1386. S8 Carbazole 2b. From 60.5 mg (0.0.17 mmol) of allene 2b, and after chromatography of the residue using hexanes/ethyl acetate (8:1) as eluent, gave compound 2b (37 mg, 62%) as a yellow solid; mp 134136 ºC; 1H NMR (300 MHz, CDCl3, 25 ºC) δ: 8.14 (s, 1H), 8.10 (d, J = 7.7 Hz, 1H), 8.05 (s, 1H), 7.38 (m, 3H), 7.287.20 (m, 8H), 6.92 (d, J = 8.7 Hz, 2H), 3.85 (s, 3H); 13C NMR (75 MHz, CDCl3, 25 ºC) δ: 159.0, 142.1, 140.1, 139.3, 138.5, 131.9 (2C), 130.7 (2C), 129.9, 128.1 (2C), 126.5, 126.2, 123.9, 123.3, 122.8, 122.7, 120.8, 119.9, 119.5, 114.7 (2C), 111.0, 55.6; IR (CH2Cl2, cm-1) ν: 3438; HRMS (ES): calcd for C25H20NO [M + H]+: 350.1539; found: 350.1534. Carbazole 2c. From 50 mg (0.16 mmol) of allene 1c, and after chromatography of the residue using hexanes/ethyl acetate (8:1) as eluent, gave compound 2c (34 mg, 70%) as a colorless solid; mp 154156 ºC; 1H NMR (300 MHz, CDCl3, 25 ºC) δ: 7.91 (d, J = 7.9 Hz, 1H), 7.85 (m, 1H), 7.67 (br s, 1H), 7.38 (d, J = 8.8 Hz, 2H), 7.18 (m, 3H), 7.09 (d, J = 8.8 Hz, 2H), 3.92 (s, 3H), 2.52 (s, 3H), 2.36 (s, 3H); 13C NMR (75 MHz, CDCl3, 25 ºC) δ: 159.0, 139.4, 137.6, 133.1, 130.9 (2C), 129.7, 128.5, 126.6, 123.9, 123.8, 121.7, 120.9, 120.1, 118.7, 114.4 (2C), 110.1, 55.4, 21.4, 20.1; IR (CH2Cl2, cm-1) ν: 3383; HRMS (ES): calcd for C21H20NO [M + H]+: 302.1539; found: 302.1526. Carbazole 2d. From 48 mg (0.15 mmol) of allene 1d, and after chromatography of the residue using hexanes/ethyl acetate (8:1) as eluent, gave compound 2d (30 mg, 63%) as a pale green solid; mp 167169 ºC; 1H NMR (300 MHz, CDCl3, 25 ºC) δ: 7.90 (d, J = 8.0 Hz, 1H), 7.63 (br s, 1H), 7.54 (d, J = 2.5 Hz, 1H), 7.37 (d, J = 8.7 Hz, 2H), 7.22 (d, J = 8.7 Hz, 1H), 7.15 (d, J = 8.1 Hz, 1H), 7.09 (d, J = 8.7 Hz, 2H), 7.00 (dd, J = 8.7, 2.5 Hz, 1H), 3.94 (s, 3H), 3.92 (s, 3H), 2.36 (s, 3H); 13C NMR (75 S9 MHz, CDCl3, 25 ºC) δ: 159.0, 153.8, 140.0, 134.3, 133.3, 130.9 (2C), 129.7, 124.2, 124.1, 121.6, 121.1, 118.8, 114.5 (2C), 111.2, 103.1, 77.3, 56.1, 55.4, 20.1; IR (CH2Cl2, cm-1) ν: 3368; HRMS (ES): calcd for C21H20NO2 [M + H]+: 318.1489; found: 318.1486. Carbazole 2e. From 34 mg (0.14 mmol) of allene 1e, and after chromatography of the residue using hexanes/ethyl acetate (8:1) as eluent, gave compound 2e (34 mg, 67%) as a colorless solid; mp 180182 ºC; 1H NMR (300 MHz, CDCl3, 25 ºC) δ: 8.18 (d, J = 1.9 Hz, 1H), 7.89 (d, J = 8.0 Hz, 1H), 7.81 (br s, 1H), 7.44 (dd, J = 8.6, 1.9 Hz, 1H), 7.36 (d, J = 8.8 Hz, 2H), 7.21 (s, 1H), 7.18 (d, J = 1.5 Hz, 1H), 7.09 (d, J = 8.8 Hz, 2H), 3.92 (s, 3H), 2.37 (s, 3H); 13C NMR (75 MHz, CDCl3, 25 ºC) δ: 159.1, 139.5, 137.9, 134.2, 130.8 (2C), 129.2, 127.9, 125.5, 124.2, 122.9, 122.4, 120.0, 118.9, 114.5 (2C), 112.0, 111.9, 55.3, 20.1; IR (CH2Cl2, cm-1) ν: 3354; HRMS (ES): calcd for C20H17BrNO [M + H]+: 366.0488; found: 366.0480. Carbazole 2f. From 30 mg (0.09 mmol) of allene 1f, and after chromatography of the residue using hexanes/ethyl acetate (12:1) as eluent, gave compound 2f (16.5 mg, 60%) as a pale brown solid; mp 136138 ºC; 1H NMR (700 MHz, CDCl3, 25 ºC) δ: 7.89 (d, J = 8.0 Hz, 1H), 7.72 (br s, 1H), 7.70 (m, 1H), 7.37 (d, J = 8.6 Hz, 2H), 7.23 (dd, J = 8.7, 4.3 Hz, 1H), 7.18 (d, J = 7.9 Hz, 1H), 7.09 (m, 3H), 3.92 (s, 3H), 2.36 (s, 3H).; 13C NMR (175 MHz, CDCl3, 25 ºC) δ: 159.0, 157.4 (d, J = 234.5 Hz), 140.2, 135.6, 134.0, 130.8 (2C), 129.4, 124.3, 124.2, 122.0, 120.7, 119.0, 114.5 (2C), 113.0 (d, J = 26.3 Hz), 110.9 (d, J = 8.8 Hz), 105.8 (d, J = 22.8 Hz), 55.4, 20.1; 19F NMR (282 MHz, CDCl3, 25 S10 °C): δ = −124.6 (s, 1F); IR (CH2Cl2, cm-1) ν: 3383; HRMS (ES): calcd for C20H17FNO [M + H]+: 306.1289; found: 306.1273. Carbazole 2g. From 15 mg (0.04 mmol) of allene 1g, and after chromatography of the residue using hexanes/ethyl acetate (8:1) as eluent, gave compound 2g (9 mg, 61%) as a pale brown oil; 1H NMR (300 MHz, CDCl3, 25 ºC) δ: 8.07 (d, J = 7.9 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H), 7.84 (s, 1H), 7.39 (m, 2H), 7.23 (m, 1H), 7.19 (d, J = 8.0 Hz, 1H), 6.65 (s, 2H), 3.98 (s, 3H), 3.88 (s, 6H), 2.39 (s, 3H); 13C NMR (175 MHz, CDCl3, 25 ºC) δ: 153.7 (2C), 139.3, 138.7, 137.2, 133.1, 133.0, 125.4, 124.4, 123.6, 121.9, 121.0, 120.2, 119.4, 119.1, 110.5, 106.6, 106.5, 61.0, 56.2 (2C), 20.1; IR (CH2Cl2, cm-1) ν: 3403; HRMS (ES): calcd for C22H22NO3 [M + H]+: 348.1594; found: 348.1611. Carbazole 2h. From 39 mg (0.13 mmol) of allene 1h, and after chromatography of the residue using toluene/ethyl acetate (10:1) as eluent, gave compound 2h (31 mg, 80%) as a pale yellow oil; 1H NMR (700 MHz, CDCl3, 25 ºC) δ: 8.06 (d, J = 7.9 Hz, 1H), 7.95 (d, J = 7.9 Hz, 1H), 7.81 (br s, 1H), 7.35 (m, 2H), 7.22 (m, 1H), 7.17 (d, J = 8.0 Hz, 1H), 7.01 (d, J = 7.8 Hz, 1H), 6.91 (m, 2H), 6.08 (m, 2H), 2.37 (s, 3H); 13C NMR (175 MHz, CDCl3, 25 ºC) δ: 148.1, 147.0, 139.3, 138.9, 133.3, 131.1, 125.3, 123.9, 123.7, 123.0, 121.9, 121.0, 120.1, 119.3, 119.0, 110.5, 110.3, 108.9, 101.2, 20.1; IR (CH2Cl2, cm-1) ν: 3442; HRMS (ES): calcd for C20H16NO2 [M + H]+: 302.1176; found: 302.1149. General procedure for the AgNPs-catalyzed preparation of dihydrocarbazoles 3a–3h. To a solution of the appropriate allene 1 (0.15 mmol) in toluene (1.4 ml) was added 1 weight% AgNO3•SiO2. The reaction mixture was stirred in the dark at room temperature under argon S11 atmosphere until the starting material disappeared, as indicated by TLC. The crude reaction was filtered with vacuum filtration and the residue was washed with toluene (3 x 2 ml). The solution was transferred into a 25 mL round-bottom flask using toluene. After removal of the solvent in vacuum, the residue was purified by column chromatography on silica gel to give analytically pure compounds. Spectroscopic and analytical data for products 3a–3h follow. Dihydrocarbazole 3a. From 42.7 mg (0.15 mmol) of allene 1a, and after chromatography of the residue using hexanes/ethyl acetate (6:1) as eluent, gave compound 3a (30 mg, 69%) as a yellow solid; mp 150152 ºC; 1H NMR (300 MHz, CDCl3, 25 ºC) δ: 7.55 (m, 1H), 7.48 (br s, 1H), 7.22 (m, 1H), 7.11 (m, 4H), 6.84 (d, J = 8.7 Hz, 2H), 5.89 (m, 1H), 4.45 (t, J = 6.2 Hz, 1H), 3.80 (s, 3H), 3.53 (m, 2H), 1.68 (m, 3H); 13C NMR (75 MHz, CDCl3, 25 ºC) δ: 158.5, 136.4, 135.2, 134.6, 133.2, 129.4 (2C), 126.8, 121.4, 120.6, 119.1, 118.2, 114.0 (2C), 110.6, 107.4, 55.2, 45.1, 23.5, 21.8; IR (CH2Cl2, cm-1) ν: 3409; HRMS (ES): calcd for C20H20NO [M + H]+: 290.1539; found: 290.1537. Dihydrocarbazole 3b. From 60 mg (0.17 mmol) of allene 1b, and after chromatography of the residue using hexanes/ethyl acetate (8:1) as eluent, gave compound 3b (32 mg, 53%) as a yellow solid; mp 132134 ºC; 1H NMR (300 MHz, CDCl3, 25 ºC) δ: 7.49 (m, 2H), 7.22 (m, 2H), 7.177.09 (m, 5H), 6.97 (d, J = 8.7 Hz, 2H), 6.61 (d, J = 8.7 Hz, 2H), 6.29 (td, J = 3.6, 1.4 Hz, 1H), 5.10 (td, J = 6.3, 1.3 Hz, 1H), 3.65 (m, 2H), 3.61 (s, 3H); 13C NMR (75 MHz, CDCl3, 25 ºC) δ: 158.3, 141.6, 138.3, 136.6, 135.4, 134.4, 131.5, 129.4 (2C), 128.1 (2C), 127.0 (2C), 126.8, 124.5, 121.7, 119.4, S12 118.4, 114.0 (2C), 110.8, 106.7, 55.2, 43.1, 24.3; IR (CH2Cl2, cm-1) ν: 3438; HRMS (ES): calcd for C25H22NO [M + H]+: 352.1696; found: 352.1705. Dihydrocarbazole 3c. From 20 mg (0.07 mmol) of allene 1c, and after chromatography of the residue using hexanes/ethyl acetate (6:1) as eluent, gave compound 3c (10 mg, 46%) as a pale brown oil; 1H NMR (700 MHz, CD3CN, 25 ºC) δ: 8.55 (br s, 1H), 7.26 (s, 1H), 7.10 (d, J = 8.7 Hz, 2H), 7.08 (d, J = 8.3 Hz, 1H), 6.88 (dd, J = 8.0, 1.9 Hz, 1H), 6.84 (d, J = 8.7 Hz, 2H), 5.87 (m, 1H), 4.46 (t, J = 5.9 Hz, 1H), 3.74 (s, 3H), 3.49 (m, 1H), 3.38 (m, 1H), 2.39 (s, 3H), 1.63 (m, 3H); 13C NMR (175 MHz, CD3CN, 25 ºC) δ: 159.9, 137.4, 136.6, 136.3, 135.1, 130.6 (2C), 129.1, 128.3, 123.8, 122.0, 119.0, 115.1 (2C), 111.7, 107.1, 56.2, 46.0, 24.5, 22.4, 21.9; IR (CH2Cl2, cm-1) ν: 3364; HRMS (ES): calcd for C21H22NO [M + H]+: 304.1696; found: 304.1711. Dihydrocarbazole 3d. From 55 mg (0.17 mmol) of allene 1d, and after chromatography of the residue using hexanes/ethyl acetate (8:1) as eluent, gave compound 3d (27 mg, 50%) as a pale brown oil; 1H NMR (700 MHz, CD3CN, 25 ºC) δ: 8.55 (br s, 1H), 7.10 (d, J = 8.7 Hz, 2H), 7.09 (d, J = 8.7 Hz, 1H), 6.98 (d, J = 2.4 Hz, 1H), 6.85 (d, J = 8.7 Hz, 2H), 6.68 (dd, J = 8.7, 2.5 Hz, 1H), 5.87 (m, 1H), 4.46 (t, J = 5.8 Hz, 1H), 3.81 (s, 3H), 3.76 (s, 3H), 3.49 (m, 1H), 3.37 (m, 1H), 1.63 (m, 3H); 13C NMR (175 MHz, CD3CN, 25 ºC) δ: 159.5, 154.7, 137.7, 136.2, 134.7, 132.6, 130.2 (2C), 128.0, 121.6, 114.7 (2C), 112.2, 111.5, 107.1, 101.3, 56.2, 55.8, 45.7, 24.2, 22.0; IR (CH2Cl2, cm-1) ν: 3372; HRMS (ES): calcd for C21H22NO2 [M + H]+: 320.1645; found: 320.1653. S13 Dihydrocarbazole 3e. From 45 mg (0.12 mmol) of allene 1e, and after chromatography of the residue using hexanes/ethyl acetate (5:1) as eluent, gave compound 3e (27 mg, 62%) as a pale yellow oil; 1H NMR (300 MHz, CD3CN, 25 ºC) δ: 8.85 (s, 1H), 7.62 (s, 1H), 7.14 (d, J = 1.3 Hz, 2H), 7.11 (d, J = 8.7 Hz, 2H), 6.85 (d, J = 8.7 Hz, 2H), 5.87 (m, 1H), 4.49 (t, J = 5.9 Hz, 1H), 3.75 (s, 3H), 3.43 (m, 2H), 1.63 (m, 3H); 13C NMR (175 MHz, CD3CN, 25 ºC) δ: 159.6, 138.6, 136.3, 135.7, 134.6, 130.2 (2C), 129.5, 124.5, 121.5, 121.4, 114.8 (2C), 113.4, 112.4, 107.1, 55.8, 45.5, 23.9, 22.0; IR (CH2Cl2, cm-1) ν: 3343; HRMS (ES): calcd for C20H19BrNO [M + H]+: 368.0645; found: 368.0646. Dihydrocarbazole 3f. From 25 mg (0.08 mmol) of allene 1f, and after chromatography of the residue using hexanes/ethyl acetate (6:1) as eluent, gave compound 3f (8 mg, 33%) as a pale yellow oil; 1H NMR (700 MHz, CD3CN, 25 ºC) δ: 8.76 (s, 1H), 7.16 (m, 2H), 7.11 (d, J = 8.7 Hz, 2H), 6.85 (d, J = 8.6 Hz, 2H), 6.82 (m, 1H), 5.87 (m, 1H), 4.47 (t, J = 5.8 Hz, 1H), 3.74 (s, 3H), 3.48 (m, 1H), 3.37 (m, 1H), 1.63 (m, 3H); 13C NMR (175 MHz, CD3CN, 25 ºC) δ: 159.5, 158.3 (d, J = 231.2 Hz), 139.1, 135.9, 134.5, 134.1, 130.2 (2C), 127.9 (d, J = 10.1 Hz), 121.4, 114.7 (2C), 112.3 (d, J = 9.8 Hz), 109.6 (d, J = 25.9 Hz), 107.5 (d, J = 4.7 Hz), 103.7 (d, J = 23.4 Hz), 55.8, 45.6, 24.0, 22.0; 19F NMR (282 MHz, CDCl3, 25 °C): δ = −125.1 (s, 1F); IR (CH2Cl2, cm-1) ν: 3411; HRMS (ES): calcd for C20H19FNO [M + H]+: 308.1445; found: 308.1448. S14 N H Me 3h O O Dihydrocarbazole 3h. From 78 mg (0.26 mmol) of allene 1h, and after chromatography of the residue using hexanes/ethyl acetate (15:1) as eluent, gave compound 3h (35 mg, 44%) as a pale yellow oil; 1H NMR (700 MHz, CD3CN, 25 ºC) δ: 8.71 (s, 1H), 7.46 (d, J = 7.8 Hz, 1H), 7.22 (d, J = 8.0 Hz, 1H), 7.05 (m, 1H), 7.01 (m, 1H), 6.78 (d, J = 7.9 Hz, 1H), 6.75 (dd, J = 7.9, 1.6 Hz, 1H), 6.65 (d, J = 1.5 Hz, 1H), 5.91 (m, 1H), 5.89 (m, 2H), 4.47 (t, J = 5.9 Hz, 1H), 3.52 (m, 1H), 3.40 (m, 1H), 1.66 (m, 3H); 13C NMR (176 MHz, CD3CN, 25 ºC) δ: 148.9, 147.4, 138.2, 137.6, 136.6, 134.4, 127.6, 122.4, 122.1, 121.9, 119.7, 118.9, 111.6, 109.2, 108.9, 107.2, 102.2, 46.0, 24.1, 22.0; IR (CH2Cl2, cm-1) ν: 3421; HRMS (ES): calcd for C20H18NO2 [M + H]+: 304.1332; found: 304.1328. General procedure for the AgNPs-catalyzed preparation of spiroindolenines 6a–6h. To a solution of the appropriate allene 1 (0.15 mmol) in dichloroethane (1.4 ml) was added 1 weight% AgNO3•SiO2. The reaction mixture was stirred in the dark at 50 ºC under argon atmosphere until the starting material disappeared, as indicated by TLC. The crude reaction was filtered with vacuum filtration and the residue was washed with dichloroethane (3 x 2 ml). The solution was transferred into a 25 mL round-bottom flask using dichloroethane. After removal of the solvent in vacuum, the residue was purified by column chromatography on silica gel to give analytically pure compounds. Spectroscopic and analytical data for products 6a–6h follow. Spiroindolenine 6a. From 45 mg (0.15 mmol) of allene 1a, and after chromatography of the residue using hexanes/ethyl acetate (8:1) as eluent, gave compound 6a (26 mg, 60%) as a pale brown oil; 1H NMR (300 MHz, CDCl3, 25 ºC) δ: 7.56(m, 2H), 7.48 (dd, J = 7.6, 1.0 Hz, 1H), 7.34 (td, J = 7.6, 1.3 S15 Hz, 1H), 7.26 (m, 1H), 6.95 (d, J = 8.7 Hz, 2H), 6.81 (d, J = 8.7 Hz, 2H), 5.85 (s, 1H), 3.84 (s, 1H), 3.79 (s, 3H), 3.04 (dq, J = 16.3, 2.2 Hz, 1H), 2.37 (dt, J = 16.3, 1.7 Hz, 1H), 1.76 (m, 3H); 13C NMR (75 MHz, CDCl3, 25 ºC) δ: 177.8, 158.6 (2C), 142.8, 131.1 (2C), 128.7 (2C), 127.8, 126.4, 125.0, 120.8, 120.5, 114.0 (2C), 61.7 (2C), 55.2, 37.3, 15.2; IR (CH2Cl2, cm-1) ν: 1509; HRMS (ES): calcd for C20H20NO [M + H]+: 290.1539; found: 290.1551. Spiroindolenine 6b. From 25 mg (0.07 mmol) of allene 1b, and after chromatography of the residue using toluene/ethyl acetate (15:1) as eluent, gave compound 6b (12 mg, 52%) as a pale yellow oil; 1H NMR (700 MHz, CDCl3, 25 ºC) δ: 7.64 (d, J = 7.7 Hz, 1H), 7.57 (s, 1H), 7.50 (d, J = 7.7 Hz, 1H), 7.38 (m, 3H), 7.26–7.16 (m, 4H), 7.03 (d, J = 8.6 Hz, 2H), 6.79 (d, J = 8.6 Hz, 2H), 6.69 (m, 1H), 4.48 (s, 1H), 3.77 (s, 3H), 3.32 (dt, J = 17.3, 2.1 Hz, 1H), 2.52 (dd, J = 17.3, 2.9 Hz, 1H); 13C NMR (175 MHz, CDCl3, 25 ºC) δ: 177.5, 158.8, 145.6, 145.1, 134.6, 131.0, 129.0, 128.5 (3C), 128.2, 127.6, 126.4 (3C), 125.9, 120.9, 120.7, 114.4 (3C), 67.2, 58.6, 55.2, 37.4; IR (CH2Cl2, cm-1) ν: 1505; HRMS (ES): calcd for C25H22NO [M + H]+: 352.1696; found: 352.1698. Spiroindolenine 6c. From 15 mg (0.05 mmol) of allene 1c, and after chromatography of the residue using toluene/ethyl acetate (12:1) as eluent, gave compound 6c (13 mg, 86%) as a pale yellow solid; mp 103105 ºC; 1H NMR (700 MHz, CDCl3, 25 ºC) δ: 7.48 (s, 1H), 7.44 (d, J = 7.8 Hz, 1H), 7.27 (m, 1H), 7.14 (d, J = 7.7, 1H), 6.94 (d, J = 8.7 Hz, 2H), 6.81 (d, J = 8.6 Hz, 2H), 5.84 (s, 1H), 3.83 (s, 1H), 3.79 (s, 3H), 3.03 (dq, J = 16.4, 2.3 Hz, 1H), 2.42 (s, 3H), 2.36 (dt, J = 16.4, 2.3 Hz, 1H), S16 1.77 (s, 3H); 13C NMR (175 MHz, CDCl3, 25 ºC) δ: 177.0, 158.6, 151.7, 146.1, 142.8, 136.3, 131.2, 128.7 (2C), 128.4, 125.0, 121.3, 120.3, 114.0 (2C), 66.9, 61.8, 55.2, 37.5, 21.5, 15.2; IR (CH2Cl2, cm- 1) ν: 1506; HRMS (ES): calcd for C21H23NO [M + H]+: 305.1774; found: 305.1763. Spiroindolenine 6d. From 33 mg (0.10 mmol) of allene 1d, and after chromatography of the residue using toluene/ethyl acetate (10:1) as eluent, gave compound 6d (24 mg, 75%) as a pale brown oil; 1H NMR (700 MHz, CDCl3, 25 ºC) δ: 7.47 (d, J = 8.4 Hz, 1H), 7.44 (s, 1H), 7.04 (d, J = 2.6 Hz, 1H), 6.94 (d, J = 8.6 Hz, 2H), 6.85 (dd, J = 8.5, 2.6 Hz, 1H), 6.81 (d, J = 8.8 Hz, 2H), 5.84 (m, 1H), 3.86 (s, 3H), 3.82 (m, 1H), 3.79 (s, 3H), 3.04 (dq, J = 16.3, 2.3 Hz, 1H), 2.36 (dt, J = 16.4, 1.7 Hz, 1H), 1.75 (m, 3H); 13C NMR (176 MHz, CDCl3, 25 ºC) δ: 175.8, 158.9, 158.7, 147.6, 142.8 (2C), 130.9, 128.7 (2C), 125.0, 121.0, 114.1 (2C), 112.0, 107.5, 67.2, 62.0, 55.7, 55.2, 37.7, 15.2; IR (CH2Cl2, cm- 1) ν: 1509; HRMS (ES): calcd for C21H22NO2 [M + H]+: 320.1645; found: 320.1654. Spiroindolenine 6e. From 24 mg (0.065 mmol) of allene 1e, and after chromatography of the residue using toluene/ethyl acetate (10:1) as eluent, gave compound 6e (9 mg, 37%) as a pale yellow oil; 1H NMR (700 MHz, CDCl3, 25 ºC) δ: 7.66 (s, 1H), 7.64 (s, 1H), 7.52 (s, 1H), 7.46 (m, 1H), 6.94 (d, J = 8.6 Hz, 2H), 6.83 (d, J = 8.6 Hz, 2H), 5.86 (s, 1H), 3.89 (s, 1H), 3.80 (s, 3H), 3.11 (m, 1H), 2.40 (m, 1H), 1.77 (s, 3H); IR (CH2Cl2, cm-1) ν: 1509; HRMS (ES): calcd for C20H19BrNO [M + H]+: 368.0644; found: 368.0643. Compound 6e is unstable in solution and a good quality 13C NMR spectrum cannot be recorded. S17 Spiroindolenine 6f. From 19 mg (0.06 mmol) of allene 1f, and after chromatography of the residue using hexanes/ethyl acetate (6:1) as eluent, gave compound 6f (15 mg, 79%) as a pale yellow oil; 1H NMR (700 MHz, CDCl3, 25 ºC) δ: 7.56 (s, 1H), 7.52 (m, 1H), 7.18 (dd, J = 8.0, 2.6 Hz, 1H), 7.04 (td, J = 8.8, 2.6 Hz, 1H), 6.95 (d, J = 8.5 Hz, 2H), 6.82 (d, J = 8.6 Hz, 2H), 5.85 (s, 1H), 3.83 (s, 1H), 3.80 (s, 3H), 3.07 (dq, J = 16.5, 2.3 Hz, 1H), 2.37 (dt, J = 16.5, 2.2 Hz, 1H), 1.76 (s, 3H); 13C NMR (175 MHz, CDCl3, 25 ºC) δ: 177.7, 162.1 (d, J = 245.3 Hz), 158.8 (2C), 142.9, 130.5, 129.6, 128.7 (3C), 124.8, 121.4 (d, J = 8.9 Hz), 114.6 (d, J = 24.0 Hz), 114.2 (2C), 108.5 (d, J = 24.8 Hz), 61.9, 55.2, 37.3, 15.1; 19F NMR (282 MHz, CDCl3, 25 °C): δ = −114.9 (s, 1F); IR (CH2Cl2, cm-1) ν: 1510; HRMS (ES): calcd for C20H19FNO [M + H]+: 308.1445; found: 308.1454. Spiroindolenine 6g. From 14 mg (0.04 mmol) of allene 1g, and after chromatography of the residue using toluene/ethyl acetate (20:1) as eluent, gave compound 6g (7.6 mg, 55%) as a pale brown oil; 1H NMR (700 MHz, CDCl3, 25 ºC) δ: 7.59 (d, J = 7.7 Hz, 1H), 7.56 (s, 1H), 7.48 (d, J = 7.4 Hz, 1H), 7.36 (t, J = 7.6 Hz, 1H), 7.27 (m, 1H), 6.23 (s, 2H), 5.90 (s, 1H), 3.84 (s, 3H), 3.79 (s, 1H), 3.78 (s, 6H), 3.07 (d, J = 16.5 Hz, 1H), 2.36 (m, 1H), 1.81 (s, 3H); 13C NMR (175 MHz, CDCl3, 25 ºC) δ: 177.6, 153.4, 145.9, 142.6, 137.0, 134.6, 129.0, 128.2, 128.0, 126.6, 125.6, 120.9, 120.4, 104.4 (2C), 67.0, 62.7, 60.9, 56.1 (2C), 37.5, 15.3; IR (CH2Cl2, cm-1) ν: 1509; HRMS (ES): calcd for C22H24NO3 [M + H]+: 350.1751; found: 350.1740. S18 Spiroindolenine 6h. From 14 mg (0.047 mmol) of allene 1h, and after chromatography of the residue using toluene/ethyl acetate (9:1) as eluent, gave compound 6h (9 mg, 64%) as a colorless oil; 1H NMR (700 MHz, CDCl3, 25 ºC) δ: 7.62 (s, 1H), 7.58 (d, J = 7.6 Hz, 1H), 7.47 (d, J = 7.7 Hz, 1H), 7.35 (td, J = 7.6, 1.4 Hz, 1H), 7.27 (m, 1H), 6.70 (d, J = 7.8 Hz, 1H), 6.55 (d, J = 1.7 Hz, 1H), 6.46 (dd, J = 7.9, 1.8 Hz, 1H), 5.95 (q, J = 1.5 Hz, 2H), 5.85 (m, 1H), 3.82 (s, 1H), 3.05 (dq, J = 16.5, 2.3 Hz, 1H), 2.39 (m, 1H), 1.77 (s, 3H); 13C NMR (175 MHz, CDCl3, 25 ºC) δ: 177.7, 148.0, 146.7, 145.6, 142.7, 132.8, 129.0, 128.2, 128.0, 126.7, 125.3, 121.0, 120.5, 108.5, 107.7, 101.0, 67.0, 62.3, 37.4, 15.1; IR (CH2Cl2, cm-1) ν: 1509; HRMS (ES): calcd for C20H18NO2 [M + H]+: 304.1332; found: 304.1338. Electron microscopy study Figure S1. TEM image (JEOL-JEM-2100) of synthesized NPsAg-SiO2 (magnification 100000x). S19 Figure S2. Individual silver nanoparticle showing its pentagonal bipyramid molecular geometry through high resolution transmission electron microscopy. TEM image (JEOL-JEM-2100) of synthesized NPsAg-SiO2 (magnification 100000x). Figure S3. Energy dispersive X-ray spectra of Si and Ag nanoparticles on Cu grid. Figure S4. SAED pattern (JEOL-JEM-2100). S20 1400 1200 1000 800 600 400 200 N or m al iz e d R a m an in te ns ity /a .u . wavenumber/cm-1 SiO 2 AgNPs AgNO 3 Figure S5. Raman spectra recorded using a wavelength of λ = 532 nm. All the Raman spectra were normalized to the maximun intensity. S21 S22 S23 N H • Me OMe 1c Me S24 N H • Me OMe MeO 1d S25 S26 S27 S28 S29 S30 S31 S32 S33 S34 N H Me OMe 2e Br S35 N H Me OMe 2f F S36 S37 S38 N H Me 2h O O S39 S40 S41 S42 S43 S44 S45 S46 N H Me OMe Br 3e S47 S48 S49 N H Me 3h O O S50 S51 S52 S53 S54 S55 6b N MeO S56 S57 S58 Compound 6e is unstable in solution and a good quality 13C NMR spectrum cannot be recorded S59 S60 S61 S62 S63 Computational Details All the calculations reported in this paper were performed with the Gaussian 09 suite of programs.1 Electron correlation was partially taken into account using the hybrid functional usually denoted as B3LYP2 in conjunction with the D3 dispersion correction suggested by Grimme et al.3 using the double- quality plus polarization def2-SVP4 basis set for all atoms. Solvents effects (solvent = dichloroethane, DCE) were taken into account using the Polarizable Continuum Model (PCM)5 during the geometry optimizations. Reactants and products were characterized by frequency calculations,6 and have positive definite Hessian matrices. Transition structures (TS’s) show only one negative eigenvalue in their diagonalized force constant matrices, and their associated eigenvectors were confirmed to correspond to the motion along the reaction coordinate under consideration using the Intrinsic Reaction Coordinate (IRC) method.7 Single-point energy refinements were carried out at the same DFT level using the much larger triple- quality plus polarization def2-TZVPP basis set for all atoms. This level is denoted PCM(DCE)-B3LYP-D3/def2-TZVPP//PCM(DCE)-B3LYP- D3/def2-SVP level. 1 Gaussian 09, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2009. 2 a) A. D. Becke, J. Chem. Phys. 1993, 98, 5648; b) C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1998, 37, 785; c) S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200. 3 S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys. 2010, 132, 154104. 4 F. Weigend, R. Alhrichs, Phys. Chem. Chem. Phys. 2005, 7, 3297. 5 a) S. Miertuš, E. Scrocco, J. Tomasi, Chem. Phys. 1981, 55, 117; b) J. L. Pascual-Ahuir, E. Silla, I. Tuñón, J. Comp. Chem. 1994, 15, 1127; c) Barone, V.; Cossi, M. J. Phys. Chem. A, 1998, 102, 1995. 6 J. W. McIver, A. K. Komornicki, J. Am. Chem. Soc. 1972, 94, 2625. 7 C. González, H. B. Schlegel, J. Phys. Chem. 1990, 94, 5523. S64 Cartesian coordinates (in Å) and total energies (in a. u.) of all the stationary points discussed in the text. All calculations have been performed at the PCM(DCE)-B3LYP-D3/def2-TZVPP//PCM(DCE)- B3LYP-D3/def2-SVP level. 1a’: E = -789.295624 C 2.623730000 0.591450000 0.733630000 C 1.410970000 0.259470000 0.056250000 C 1.291510000 0.583210000 -1.310660000 C 2.350090000 1.217700000 -1.954400000 C 3.541040000 1.538300000 -1.262360000 C 3.693390000 1.228970000 0.087040000 C 1.258270000 -0.406890000 2.209140000 H 0.380990000 0.334950000 -1.856490000 H 2.263010000 1.471850000 -3.014040000 H 4.355810000 2.035550000 -1.795170000 H 4.612220000 1.472020000 0.626150000 H 3.198260000 0.275960000 2.759750000 H 0.957400000 -0.800240000 3.178990000 C 0.551820000 -0.382670000 1.025630000 C 1.013650000 -3.123430000 -1.429170000 C -0.853770000 -0.906780000 0.848020000 C 0.024310000 -2.656790000 -0.707760000 H 1.753680000 -3.816720000 -1.010750000 H 1.150010000 -2.824100000 -2.475480000 C -0.968530000 -2.188510000 0.016190000 H -1.210480000 -1.181950000 1.856540000 C -1.792710000 0.204410000 0.356350000 C -2.202410000 1.199130000 1.258800000 C -2.225540000 0.292910000 -0.974060000 C -3.016410000 2.256120000 0.844580000 H -1.868280000 1.146230000 2.299240000 C -3.041210000 1.350090000 -1.394660000 H -1.924260000 -0.475340000 -1.690150000 C -3.438950000 2.336650000 -0.487940000 H -3.323480000 3.019700000 1.564300000 H -3.366490000 1.400470000 -2.437210000 H -4.076100000 3.162260000 -0.815200000 C -2.294580000 -2.915570000 0.105450000 H -3.124620000 -2.253510000 -0.190190000 H -2.315900000 -3.809570000 -0.533150000 H -2.486860000 -3.226370000 1.147230000 N 2.496710000 0.171750000 2.037890000 [Ag(PMe3)]+: E = -608.129855 Ag -1.376410000 0.000020000 0.000160000 P 1.030140000 0.000310000 0.000710000 C 1.775590000 -1.239770000 1.126400000 H 1.447160000 -2.246590000 0.830680000 H 2.874260000 -1.181990000 1.075660000 H 1.444580000 -1.045770000 2.156830000 C 1.775470000 1.596820000 0.508230000 H 2.874200000 1.525010000 0.480760000 H 1.442670000 2.390380000 -0.176460000 H 1.449060000 1.846520000 1.528090000 C 1.773570000 -0.357540000 -1.636350000 S65 H 2.872150000 -0.343920000 -1.560250000 H 1.441740000 -1.347370000 -1.982000000 H 1.445810000 0.401380000 -2.361240000 INT1: E = -1397.451058 C -3.807107000 -2.276420000 -0.446476000 C -3.026438000 -1.174914000 0.018356000 C -2.780649000 -1.059310000 1.402412000 C -3.304116000 -2.015669000 2.267809000 C -4.074471000 -3.098105000 1.783454000 C -4.335017000 -3.242252000 0.423219000 C -3.214061000 -1.053112000 -2.232072000 H -2.188838000 -0.229853000 1.790925000 H -3.119197000 -1.930010000 3.341676000 H -4.472202000 -3.833051000 2.487913000 H -4.928722000 -4.076573000 0.042367000 H -4.407435000 -2.804091000 -2.419809000 H -3.172347000 -0.785064000 -3.286618000 C -2.654818000 -0.406896000 -1.149420000 C 0.413723000 -1.608929000 0.077413000 C -1.843895000 0.863849000 -1.232339000 C 0.112968000 -0.423911000 -0.457166000 H 0.541193000 -2.496004000 -0.556565000 H 0.319145000 -1.775162000 1.158334000 C -0.336142000 0.690246000 -0.986596000 H -1.917450000 1.216104000 -2.275623000 C -2.444047000 1.970957000 -0.355368000 C -3.614309000 2.614590000 -0.787906000 C -1.898169000 2.334570000 0.883295000 C -4.226468000 3.592914000 -0.001223000 H -4.054563000 2.335710000 -1.749462000 C -2.508364000 3.314674000 1.674863000 H -0.985263000 1.849287000 1.236862000 C -3.675230000 3.946366000 1.236431000 H -5.137208000 4.082691000 -0.355476000 H -2.067665000 3.583378000 2.638383000 H -4.152724000 4.711568000 1.853479000 C 0.543264000 1.843749000 -1.407788000 H 0.205095000 2.775623000 -0.929459000 H 1.600182000 1.682531000 -1.155327000 H 0.461795000 1.987586000 -2.497922000 Ag 2.581526000 -0.711623000 0.055437000 P 4.843275000 0.130681000 0.138304000 C 4.936005000 1.892850000 0.639879000 H 4.502348000 2.011496000 1.643557000 H 5.982924000 2.233545000 0.648410000 H 4.357474000 2.502515000 -0.069379000 C 5.735013000 0.069548000 -1.463668000 H 6.747759000 0.487375000 -1.352378000 H 5.804498000 -0.973519000 -1.804983000 H 5.178812000 0.651421000 -2.213109000 C 5.952728000 -0.737945000 1.312559000 H 6.954058000 -0.280048000 1.300247000 H 5.533134000 -0.674089000 2.327036000 H 6.031056000 -1.797322000 1.027674000 N -3.899872000 -2.170153000 -1.815552000 TS1: E = -1397.423195 C -3.383487000 -2.503656000 -0.312550000 S66 C -2.986330000 -1.200626000 0.084508000 C -3.428196000 -0.719354000 1.328793000 C -4.234597000 -1.538295000 2.119712000 C -4.606054000 -2.832862000 1.703913000 C -4.180864000 -3.337471000 0.476234000 C -2.124219000 -1.685989000 -1.975747000 H -3.150805000 0.275123000 1.674522000 H -4.586789000 -1.166662000 3.084918000 H -5.235359000 -3.448546000 2.350562000 H -4.457928000 -4.338660000 0.140136000 H -2.940360000 -3.609148000 -2.094914000 H -1.633594000 -1.668414000 -2.948159000 C -2.103038000 -0.680525000 -0.974634000 C -0.169684000 -1.240821000 -0.242109000 C -1.730909000 0.759019000 -1.322355000 C 0.470252000 -0.048624000 -0.660638000 H 0.038282000 -2.177689000 -0.772865000 H -0.398789000 -1.393779000 0.821269000 C -0.201217000 0.952342000 -1.243387000 H -2.034608000 0.929870000 -2.370148000 C -2.491020000 1.781798000 -0.477882000 C -3.792704000 2.156332000 -0.842751000 C -1.940977000 2.322076000 0.694245000 C -4.534224000 3.037402000 -0.050615000 H -4.235593000 1.742706000 -1.753321000 C -2.677733000 3.207260000 1.487984000 H -0.929856000 2.035569000 0.993600000 C -3.978823000 3.565525000 1.120159000 H -5.549070000 3.312951000 -0.348740000 H -2.233420000 3.616665000 2.398877000 H -4.556106000 4.255736000 1.740384000 C 0.352498000 2.239004000 -1.784217000 H -0.097238000 3.112560000 -1.283737000 H 1.443554000 2.293724000 -1.665374000 H 0.115300000 2.338145000 -2.858194000 Ag 2.549453000 -0.124525000 -0.129734000 P 4.893817000 -0.151509000 0.472311000 C 5.685987000 -1.808409000 0.442446000 H 5.598079000 -2.235721000 -0.567296000 H 6.750020000 -1.734153000 0.716808000 H 5.171035000 -2.472495000 1.152045000 C 5.262362000 0.481551000 2.156854000 H 6.345369000 0.449086000 2.354012000 H 4.906397000 1.518893000 2.241622000 H 4.736052000 -0.133086000 2.901867000 C 5.965043000 0.864565000 -0.620718000 H 7.013322000 0.817670000 -0.286826000 H 5.892510000 0.490792000 -1.652684000 H 5.621080000 1.909080000 -0.599893000 N -2.836492000 -2.745194000 -1.571303000 TS1’: E= -1397.421923 C -3.266466000 -2.605354000 -0.166790000 C -3.273685000 -1.174589000 -0.058898000 C -4.226985000 -0.572908000 0.804554000 C -5.099735000 -1.382197000 1.513999000 C -5.055414000 -2.794870000 1.401571000 C -4.142122000 -3.423176000 0.567037000 C -1.645375000 -1.834410000 -1.515171000 H -4.285731000 0.508235000 0.905986000 S67 H -5.839384000 -0.924064000 2.174493000 H -5.758465000 -3.399581000 1.979643000 H -4.106903000 -4.510089000 0.470093000 H -2.089329000 -3.913000000 -1.353019000 H -1.086303000 -1.865748000 -2.449140000 C -2.254482000 -0.688899000 -0.945872000 C 0.112280000 -1.533942000 -0.378728000 C -1.753895000 0.690129000 -1.248831000 C 0.515545000 -0.205492000 -0.625200000 H 0.594523000 -2.347829000 -0.931376000 H -0.199153000 -1.824250000 0.635023000 C -0.205792000 0.843234000 -1.025920000 H -1.906612000 0.870575000 -2.328482000 C -2.509283000 1.771627000 -0.484009000 C -3.569093000 2.459602000 -1.088063000 C -2.190403000 2.057830000 0.852834000 C -4.309839000 3.403538000 -0.367582000 H -3.826984000 2.247064000 -2.129288000 C -2.924596000 3.001504000 1.574288000 H -1.365110000 1.524544000 1.331999000 C -3.991389000 3.675100000 0.966475000 H -5.137810000 3.927907000 -0.851297000 H -2.667294000 3.210210000 2.615772000 H -4.568529000 4.412152000 1.530308000 C 0.323226000 2.228607000 -1.295710000 H -0.052555000 2.960747000 -0.563966000 H 1.420834000 2.250342000 -1.274961000 H -0.011812000 2.578683000 -2.287562000 Ag 2.626112000 -0.148836000 -0.112214000 P 4.976218000 -0.052730000 0.458608000 C 6.070209000 -1.009061000 -0.664660000 H 5.964910000 -0.624769000 -1.689875000 H 7.120785000 -0.921112000 -0.346656000 H 5.771354000 -2.067529000 -0.652357000 C 5.384934000 -0.701713000 2.127501000 H 6.467686000 -0.629771000 2.315318000 H 4.841755000 -0.121821000 2.888070000 H 5.071237000 -1.753722000 2.195920000 C 5.704537000 1.632720000 0.448365000 H 6.771579000 1.592533000 0.717926000 H 5.597694000 2.069197000 -0.555475000 H 5.168523000 2.268203000 1.168441000 N -2.301785000 -2.964938000 -1.066818000 INT2: E = -1397.436893 C 3.632695000 -2.340517000 0.242376000 C 3.058496000 -1.173854000 -0.286755000 C 3.684477000 -0.549086000 -1.364186000 C 4.867984000 -1.109457000 -1.865028000 C 5.421096000 -2.274915000 -1.310461000 C 4.803446000 -2.920865000 -0.233931000 C 1.775274000 -1.985434000 1.461127000 H 3.270300000 0.358010000 -1.805142000 H 5.372192000 -0.627174000 -2.705363000 H 6.343927000 -2.686023000 -1.724809000 H 5.216617000 -3.829776000 0.206467000 H 2.976564000 -3.604957000 1.868834000 H 1.021262000 -2.155182000 2.230951000 C 1.791710000 -0.872732000 0.475993000 C 0.448858000 -0.914382000 -0.360298000 S68 C 1.655462000 0.501627000 1.256495000 C -0.538592000 -0.093016000 0.445830000 H 0.134990000 -1.951446000 -0.559473000 H 0.649441000 -0.459238000 -1.346783000 C 0.136126000 0.661789000 1.340366000 H 2.111762000 0.403447000 2.256143000 C 2.364336000 1.645713000 0.547450000 C 3.677596000 1.988314000 0.904677000 C 1.751520000 2.339312000 -0.508398000 C 4.368703000 2.992089000 0.220335000 H 4.168294000 1.453284000 1.722624000 C 2.440894000 3.342206000 -1.197106000 H 0.725066000 2.090113000 -0.787394000 C 3.752561000 3.670284000 -0.836980000 H 5.391326000 3.244347000 0.512217000 H 1.949911000 3.872160000 -2.017383000 H 4.290601000 4.454947000 -1.374802000 C -0.402950000 1.681848000 2.299293000 H 0.003741000 2.684882000 2.077392000 H -1.500450000 1.737223000 2.251501000 H -0.109570000 1.450554000 3.339071000 Ag -2.609374000 -0.126842000 0.048236000 P -4.980685000 -0.189714000 -0.436924000 C -5.759912000 1.448833000 -0.735150000 H -5.263669000 1.939472000 -1.585498000 H -6.833425000 1.335282000 -0.953410000 H -5.632981000 2.080275000 0.156590000 C -6.031384000 -0.926416000 0.879849000 H -7.091475000 -0.920410000 0.581030000 H -5.709781000 -1.962003000 1.064786000 H -5.910223000 -0.350188000 1.809015000 C -5.438109000 -1.156313000 -1.933018000 H -6.527868000 -1.135973000 -2.091182000 H -4.933067000 -0.728965000 -2.811940000 H -5.106634000 -2.197972000 -1.809846000 N 2.797468000 -2.773935000 1.304041000 INT2’: E = -1397.435124 C -3.328057000 -2.582509000 -0.047727000 C -3.425739000 -1.137257000 -0.161414000 C -4.600980000 -0.477090000 0.325305000 C -5.599984000 -1.237619000 0.878940000 C -5.476813000 -2.661963000 0.984240000 C -4.365960000 -3.346092000 0.538484000 C -1.381949000 -1.868579000 -1.009205000 H -4.693935000 0.604785000 0.248739000 H -6.507798000 -0.759832000 1.251772000 H -6.298388000 -3.223269000 1.436253000 H -4.283349000 -4.430616000 0.623524000 H -1.845320000 -3.955921000 -0.593913000 H -1.092287000 -1.967905000 -2.069432000 C -2.254913000 -0.698184000 -0.773260000 C -0.053367000 -1.645766000 -0.193097000 C -1.726873000 0.644962000 -1.121563000 C 0.574771000 -0.313613000 -0.510015000 H 0.607917000 -2.489381000 -0.441289000 H -0.283463000 -1.732576000 0.884038000 C -0.172961000 0.717138000 -0.948551000 H -1.904748000 0.766138000 -2.209187000 C -2.446281000 1.773837000 -0.397934000 S69 C -3.321683000 2.629560000 -1.077494000 C -2.259967000 1.946217000 0.982632000 C -4.017897000 3.629192000 -0.387523000 H -3.469229000 2.507573000 -2.154063000 C -2.952142000 2.942191000 1.673864000 H -1.567627000 1.287908000 1.514655000 C -3.838275000 3.784827000 0.990224000 H -4.702235000 4.286948000 -0.929182000 H -2.801767000 3.062982000 2.749617000 H -4.381975000 4.563804000 1.530416000 C 0.369158000 2.079041000 -1.314964000 H 0.021395000 2.859309000 -0.617318000 H 1.467934000 2.082971000 -1.314890000 H 0.022039000 2.383721000 -2.318808000 Ag 2.667740000 -0.184115000 -0.111626000 P 5.032242000 -0.059181000 0.389008000 C 6.124398000 -0.987710000 -0.761877000 H 5.992490000 -0.598652000 -1.782330000 H 7.179805000 -0.884600000 -0.464537000 H 5.844215000 -2.051447000 -0.752841000 C 5.509229000 -0.704443000 2.043400000 H 6.594718000 -0.604794000 2.201267000 H 4.973277000 -0.142335000 2.822366000 H 5.225256000 -1.764601000 2.117102000 C 5.738768000 1.637471000 0.372296000 H 6.812664000 1.613005000 0.615311000 H 5.599700000 2.080024000 -0.625039000 H 5.210612000 2.260024000 1.109479000 N -2.163169000 -2.993398000 -0.561282000 TS2: E = -1397.418347 C -3.805012000 -1.228972000 -0.838945000 C -2.538754000 -1.573055000 -0.282565000 C -2.478219000 -2.193341000 0.982774000 C -3.666835000 -2.449088000 1.652276000 C -4.912927000 -2.091152000 1.084008000 C -5.004399000 -1.480200000 -0.164366000 C -2.231031000 -0.502232000 -2.263050000 H -1.515250000 -2.457393000 1.424829000 H -3.646751000 -2.925735000 2.634508000 H -5.829404000 -2.299253000 1.641237000 H -5.967317000 -1.196938000 -0.592436000 H -4.292135000 -0.256176000 -2.675992000 H -1.833057000 -0.174721000 -3.221315000 C -1.534501000 -1.118797000 -1.194799000 C -0.055935000 -1.228212000 -1.050453000 C -1.547654000 1.315615000 -1.046338000 C 0.634273000 0.080225000 -0.648296000 H 0.390238000 -1.576952000 -1.998510000 H 0.176228000 -2.008443000 -0.308747000 C -0.109053000 1.207644000 -0.671318000 H -1.728921000 1.837966000 -1.994259000 C -2.603992000 1.506289000 -0.078457000 C -3.849697000 2.038446000 -0.490617000 C -2.444680000 1.109945000 1.271356000 C -4.901056000 2.160846000 0.413376000 H -3.979927000 2.355876000 -1.528137000 C -3.496546000 1.236257000 2.171324000 H -1.486104000 0.695602000 1.589097000 C -4.728242000 1.751411000 1.742143000 S70 H -5.859348000 2.570343000 0.086656000 H -3.367470000 0.922209000 3.209119000 H -5.555979000 1.840073000 2.449962000 C 0.434972000 2.595313000 -0.354463000 H -0.090977000 3.041355000 0.507534000 H 1.507319000 2.539830000 -0.118868000 H 0.299985000 3.289800000 -1.202565000 Ag 2.698751000 -0.022539000 -0.161981000 P 5.053923000 -0.154522000 0.376207000 C 5.725980000 1.312108000 1.258268000 H 5.181048000 1.449124000 2.204026000 H 6.799032000 1.183058000 1.469782000 H 5.581502000 2.208615000 0.637396000 C 6.171170000 -0.331083000 -1.073560000 H 7.223455000 -0.375934000 -0.751672000 H 5.916401000 -1.251344000 -1.619948000 H 6.031416000 0.526924000 -1.747585000 C 5.534733000 -1.561322000 1.458292000 H 6.618911000 -1.551614000 1.652515000 H 4.991862000 -1.489416000 2.412309000 H 5.260102000 -2.507443000 0.968938000 N -3.575793000 -0.621735000 -2.059627000 INT3: E = -1397.435064 C -3.902873000 -1.241028000 -0.742000000 C -2.684473000 -1.827459000 -0.216108000 C -2.749853000 -2.792762000 0.835994000 C -3.983329000 -3.139592000 1.325053000 C -5.177618000 -2.548075000 0.791394000 C -5.166489000 -1.614295000 -0.223679000 C -2.160606000 -0.218577000 -1.813077000 H -1.832697000 -3.230308000 1.234055000 H -4.073731000 -3.869423000 2.131427000 H -6.137946000 -2.852355000 1.215436000 H -6.086207000 -1.172578000 -0.608572000 H -4.264773000 0.235615000 -2.175370000 H -1.814016000 -0.357979000 -2.850174000 C -1.623121000 -1.258137000 -0.899555000 C -0.164979000 -1.391769000 -0.750974000 C -1.627531000 1.184575000 -1.317466000 C 0.553032000 -0.023914000 -0.733552000 H 0.226042000 -1.967505000 -1.611491000 H 0.080997000 -1.989541000 0.140286000 C -0.124317000 1.107501000 -1.028528000 H -1.796653000 1.876142000 -2.158613000 C -2.434713000 1.702968000 -0.132470000 C -3.466811000 2.633171000 -0.333673000 C -2.198565000 1.233624000 1.169283000 C -4.250276000 3.077958000 0.735479000 H -3.659558000 3.015221000 -1.340562000 C -2.981951000 1.673087000 2.240401000 H -1.385253000 0.526523000 1.344717000 C -4.012043000 2.595211000 2.026701000 H -5.047314000 3.804801000 0.559407000 H -2.784037000 1.295616000 3.246774000 H -4.623336000 2.940727000 2.864131000 C 0.510516000 2.481785000 -1.038120000 H -0.011190000 3.161328000 -0.341274000 H 1.570865000 2.442757000 -0.751475000 H 0.439704000 2.945011000 -2.038675000 S71 Ag 2.612922000 -0.103560000 -0.202304000 P 4.948827000 -0.201280000 0.416750000 C 5.477513000 1.083785000 1.620734000 H 4.891086000 0.981144000 2.545736000 H 6.549227000 0.981959000 1.853075000 H 5.288982000 2.080409000 1.194947000 C 6.132205000 0.009422000 -0.974866000 H 7.171200000 -0.035363000 -0.612090000 H 5.968793000 -0.786863000 -1.715866000 H 5.955928000 0.981047000 -1.459558000 C 5.491659000 -1.772653000 1.201709000 H 6.562950000 -1.731595000 1.453936000 H 4.906869000 -1.943960000 2.117529000 H 5.311385000 -2.607553000 0.508405000 N -3.597046000 -0.366533000 -1.706454000 INT4: E = -1397.507785 C 3.731910000 0.146190000 -0.650442000 C 3.350552000 -0.961835000 0.166979000 C 4.063228000 -2.171328000 0.059005000 C 5.118465000 -2.253053000 -0.847392000 C 5.478180000 -1.146205000 -1.649431000 C 4.792970000 0.065140000 -1.562319000 C 1.980198000 0.785872000 0.607102000 H 3.790967000 -3.031084000 0.676786000 H 5.679932000 -3.185948000 -0.942343000 H 6.310498000 -1.240816000 -2.351532000 H 5.071057000 0.921006000 -2.181635000 H 2.883868000 2.097048000 -0.807713000 C 2.229909000 -0.520735000 0.956596000 C 1.442344000 -1.235157000 2.005032000 C 0.894568000 1.665580000 1.148371000 C 0.241225000 -0.428415000 2.444408000 H 2.058571000 -1.422086000 2.906797000 H 1.129663000 -2.239612000 1.670362000 C -0.010650000 0.875790000 2.107695000 H 1.352095000 2.459199000 1.770428000 C 0.101564000 2.372371000 0.043824000 C -0.372712000 3.679015000 0.230466000 C -0.191161000 1.714777000 -1.162703000 C -1.142865000 4.307479000 -0.753521000 H -0.137129000 4.212145000 1.155438000 C -0.958459000 2.342090000 -2.149292000 H 0.204797000 0.711755000 -1.344381000 C -1.442600000 3.638522000 -1.944798000 H -1.504944000 5.325473000 -0.589942000 H -1.169386000 1.818767000 -3.084808000 H -2.040714000 4.129976000 -2.715950000 C -1.062471000 1.682051000 2.831219000 H -1.722722000 2.219616000 2.135167000 H -1.676206000 1.051073000 3.488669000 H -0.564920000 2.447724000 3.450970000 Ag -1.448870000 -0.731906000 0.735836000 P -3.022899000 -1.636202000 -0.846179000 C -2.872653000 -0.909925000 -2.522453000 H -1.858159000 -1.091318000 -2.906753000 H -3.611285000 -1.360648000 -3.203232000 H -3.037752000 0.175225000 -2.462737000 C -4.783792000 -1.388707000 -0.397900000 H -5.438387000 -1.812137000 -1.175518000 S72 H -4.989884000 -1.881684000 0.563206000 H -4.985690000 -0.312562000 -0.294715000 C -2.864344000 -3.443562000 -1.115764000 H -3.612737000 -3.789183000 -1.845763000 H -1.855223000 -3.666155000 -1.492345000 H -3.011590000 -3.971216000 -0.162036000 N 2.885047000 1.192791000 -0.352299000 H -0.360094000 -0.867192000 3.249947000 3a’: E = -789.348858 C 2.210587000 -0.911718000 -0.534242000 C 2.471970000 0.315519000 0.152476000 C 3.751173000 0.533600000 0.698463000 C 4.725399000 -0.453733000 0.556966000 C 4.446385000 -1.660078000 -0.123900000 C 3.189134000 -1.904196000 -0.677862000 C 0.330889000 0.323637000 -0.575772000 H 3.974188000 1.464381000 1.227090000 H 5.721887000 -0.295819000 0.977894000 H 5.229664000 -2.416736000 -0.218694000 H 2.972790000 -2.836746000 -1.204799000 H 0.418346000 -1.618308000 -1.449786000 C 1.251815000 1.079180000 0.109730000 C 0.928344000 2.432311000 0.656067000 C -1.098269000 0.687225000 -0.837567000 C -0.485915000 2.840035000 0.330477000 H 1.627582000 3.194569000 0.259873000 H 1.079462000 2.463317000 1.753132000 C -1.392602000 2.099330000 -0.330624000 H -1.280435000 0.678494000 -1.929455000 C -2.048202000 -0.343668000 -0.220145000 C -2.946093000 -1.072560000 -1.010143000 C -2.028012000 -0.569215000 1.165662000 C -3.809605000 -2.010773000 -0.429952000 H -2.973400000 -0.903407000 -2.090564000 C -2.887355000 -1.502683000 1.747938000 H -1.328296000 -0.002337000 1.785959000 C -3.782622000 -2.228111000 0.950319000 H -4.504944000 -2.571358000 -1.060302000 H -2.860344000 -1.667249000 2.828380000 H -4.455402000 -2.959516000 1.405394000 C -2.778979000 2.604481000 -0.630923000 H -3.546409000 1.958829000 -0.171195000 H -2.928309000 3.631704000 -0.267415000 H -2.972895000 2.590473000 -1.718383000 N 0.902845000 -0.871840000 -0.967547000 H -0.781645000 3.841090000 0.663888000