Supporting Information. Carbene Transfer from Triazolylidene Gold Complexes as a Potent Strategy for Inducing High Catalytic Activity

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1 Supporting Information Carbene Transfer from Triazolylidene Gold Complexes as a Potent Strategy for Inducing High Catalytic Activity Daniel Canseco-Gonzalez, Ana Petronilho, Helge Mueller-Bunz, Kohsuke Ohmatsu, Takashi Ooi, and Martin Albrecht* 1. Experimental procedures for the new triazoles and triazolium salts 1a h... S1 2. Dynamic light scattering results... S7 3. Time-conversion profile for complexes 2b and 2d... S8 4. Crystallographic details... S8 1. Experimental procedures for the new triazoles and triazolium salts 1a h 1-(3,4,5,-trimethoxyphenyl)-4-(4-methoxyphenyl)-1,2,3-triazole (pre 1b), S1 and the triazolium salts 1a, S2 1c, S3 and 1g S4 were prepared as described. All solvents used for the reactions were purified using an alumina/catalyst column system (Thermovac Co.). Ag 2 O was freshly prepared according to literature procedures. S5 All other reagents are commercially available and were used as received. Microwave reactions were carried out in a Biotage Initiator 2.5, operating at 100 W irradiation power. Unless specified otherwise, NMR spectra were recorded at 25 C on Varian Innova spectrometers operating at 300, 400 or 500 MHz ( 1 H NMR) and 75, 100 or 125 MHz ( 13 C{ 1 H} NMR), respectively. Chemical shifts (δ in ppm, coupling constants J in Hz) were referenced to residual solvent resonances. Assignments are based on homo- and heteronuclear shift correlation spectroscopy. Elemental analyses were performed by the Microanalytical Laboratory at University College Dublin, Ireland, by using an Exeter Analytical CE-440 Elemental Analyzer. (S1) Pagliai, F.; Pirali, T.; Del Grosso, E.; Brisco, R. D.; Tron, G. C.; Sorba, G.; Genazzani, A. A. J. Med. Chem. 2006, 49, (S2) Nakamura, T.; Ogata, K.; Fukuzawa, S. Chem. Lett. 2010, 39, (S3) Donnelly, K. F.; Lalrempuia, R.; Müller-Bunz, H.; Albrecht, M. Organometallics 2012, 31, (S4) Ohmatsu, K.; Hamajima, Y.; Ooi, T. J. Am. Chem. Soc. 2012, 134, (S5) Huang, W.; Zhang, R.; Zou, G.; Tang, J.; Sun, J. J. Organomet. Chem. 2007, 692, S1

2 1,4-Di-tert-butyl-1,2,3-triazole. Freshly prepared tert-butyl azide S6 (376 mg, 3.79 mmol), and tert-butyl acetylene (249 mg, 3.03 mmol) were suspended in a mixture of water (7 ml) and THF (7 ml). Copper sulphate (14.0 mg, 0.07 mmol), and sodium ascorbate (120 mg, 0.75 mmol) were added and the mixture stirred for 6 hours at 100 C under microwave irradiation. After cooling, all volatiles were removed by evaporation and the residue was extracted with CH 2 Cl 2 (2 50 ml). The combined organic phases were washed with water (2 30 ml), brine (2 25 ml), dried over MgSO 4, and evaporated to dryness. The residue was washed with pentane (50 ml) and purified by flash chromatography (SiO 2 ; CH 2 Cl 2 /Et 2 O 2:1) to give the pure triazole as a white powder (467 mg, 85%). 1 H NMR (CDCl 3, 500 MHz): δ 7.27 (s, 1H, H trz ), 1.65, 1.35 (2 s, 9H, C-CH 3 ). 13 C{ 1 H} NMR (CDCl 3, 125 MHz): δ (C trz tbu), (C trz -H), 58.9, 30.9 (2 CMe 3 ), 30.7, 30.3 (2 C-CH 3 ). Anal. Calcd for C 10 H 19 N 3 (181.27): C, 66.26; H, 10.56; N, Found: C, 65.82; H, 10.62; N, Adamantyl-4-phenyl-1,2,3-triazole. 1-Adamantyl azide (500 mg, 2.82 mmol), and phenyl acetylene (294 mg, 2.88 mmol) were suspended in a mixture of water (7 ml) and THF (7 ml). CuSO 4 (90.0 mg, 0.57 mmol), and sodium ascorbate (112 mg, 0.57 mmol) were added and the mixture was stirred for 6 h at 100 C under microwave irradiation. After cooling, all volatiles were removed by evaporation and the residue was extracted with CH 2 Cl 2 (2 50 ml). The combined organic phases were washed with aqueous NH 4 OH 25% (2 50 ml), H 2 O (2 50 ml), brine (2 30 ml), dried over MgSO 4, and evaporated to dryness. The residue was washed with pentane (50 ml) and purified by flash chromatography (SiO 2 ; Et 2 O) to give the pure triazole as a white powder (500 mg, 64%). 1 H NMR (CDCl 3, 500 MHz): δ 7.84 (d, 3 J HH = 7.5 Hz, 2H Ar ), 7.81 (s, 1H, H trz ), 7.41 (t, 3 J HH = 7.5 Hz, 2H Ar ), 7.31 (t, 3 J HH = 7.5 Hz, 1H Ar ), 2.30 (m, 9H, adamantyl), 1.82 (m, 6H, adamantyl). 13 C{ 1 H} NMR (CDCl 3, 125 MHz): δ (C trz Ph), (C Ph ), (C Ph ), (C Ph ), (C trz -H), (C Ph ), 59.8 (C ada -N), 43.3 (C ada ), 36.2 (C ada ), 29.7 (C ada ). Anal. Calcd for C 18 H 21 N 3 (279.38): C, 77.38; H, 7.58; N, Found: C, 77.24; H, 7.58; N, (S6) Bottaro, J. C.; Penwell, P. E.; Schmitt, R. J. Synth. Commun. 1997, 27, S2

3 1-Adamantyl-4-tert-butyl-1,2,3-triazole. 1-Adamantyl azide (500 mg, 2.82 mmol), and tertbutyl alkyne (302 mg, 3.67 mmol) were suspended in a mixture of water (7 ml) and THF (7 ml). Copper sulphate (90.0 mg, 0.57 mmol), and sodium ascorbate (112 mg, 0.57 mmol) and the mixture was stirred hours at 100 C under microwave irradiation. After cooling, all volatiles were removed by evaporation and the residue was extracted with CH 2 Cl 2 (2 50 ml). The combined organic phases were washed with aqueous NH 4 OH 25% (2 50 ml), H 2 O (2 50 ml), brine (2 30 ml), dried over MgSO 4 and evaporated to dryness. The residue was washed with pentane (50 ml) and purified by flash chromatography (SiO 2 ; Et 2 O) to give the pure triazole as a white powder (550 mg, 75%). 1 H NMR (CDCl 3, 400 MHz): δ 7.28 (s, 1H, H trz ), 2.23 (m, 9H, H ada ), 1.78 (s, 6H, H ada ), 1.34 (s, 9H, C-CH 3 ). 13 C{ 1 H} NMR (CDCl 3, 100 MHz): δ (C trz -tbu), (C trz -H), 59.2 (C ada -N), 43.2 (C ada ), 36.2 (C ada ), 30.9 (CMe 3 ), 30.7 (C-CH 3 ), 29.7 (C-CH 3 ). Anal. Calcd for C 16 H 25 N 3 (259.38): C, 74.09; H, 9.71; N, Found: C, 73.88; H, 9.91; N, Mesityl-4-tert-butyl-methylcarbamate-1,2,3-triazole. Mesityl azide (800 mg, 4.9 mmol) and a solution of freshly synthesized t-butyl prop-2-ynylcarbamate S7 (798 mg, 4.9 mmol) in THF (7 ml) were suspended in a mixture of water (7.0 ml) and THF (7.0 ml). Sodium ascorbate (194 mg, 1.0 mmol) and CuSO 4 (24 mg, 0.1 mmol) were added and the mixture was stirred for 6 h at 100 C under microwave irradiation. All volatiles were evaporated and the residue was extracted with CH 2 Cl 2 (2 50 ml). The combined organic phases were washed with H 2 O (2 50 ml), brine (2 30 ml), dried over MgSO 4, and evaporated to dryness. The residue was washed with pentane (300 ml) to afford 1a as an off-white solid (1.45 g, 93%). 1 H NMR (CDCl 3, 400 MHz): δ 7.57 (s, 1H, H trz ) 6.98 (s, 2H, H Ar ), 5.19 (t, 3 J HH = 6.2 Hz, 1H, NH), 4.47 (d, 3 J HH = 6.2 Hz, 2H, CH 2 N), 2.33 (s, 3H, Ar CH 3 ), 1.93 (s, 6H, Ar CH 3 ), 1.43 (s, 9H, CH 3 Boc ). 13 C{1H} NMR (CDCl 3, 100 MHz): δ (N C=O), (C trz alkyl), 140.2, 135.2, 133.6, (4 C Mes ), (S7) The carbamate was prepared from propargylamine and (BOC) 2 O according to a published procedure (Duan, J.; Xue, C. B.; Sheppeck, J.; Jiang, B.; Chen, L. (Bristol Myers Squibb), US2004/ A1, 2004). Accordingly, propargylamine (5.0 g, 55 mmol) was added dropwise to a solution of (BOC) 2 O (20.5 g, 0.11 mol) in THF (80 ml) and stirred for 12 h. Volatiles were evaporated and the residue redissolved in Et 2 O (100 ml) and washed with H 2 O (100 ml) and brine (100 ml), dried over Na 2 SO 4 and evaporated to dryness. Purification by column chromatography (SiO 2, EtOAc/hexane 1:9) gave pure BOC-protected propargylamine as a white solid (1.29 g, 18%). 1 H NMR (CDCl 3, 400 MHz): δ 4.75 (s, 1H, CCH), 3.90 (d, 3 J HH = 2.7 Hz, 2H, NCH 2 ), 2.20 (t, 3 J HH = 2.7 Hz, 1H, NH), 1.43 (s, 9H, CH 3 ). 13 C{1H} NMR (CDCl 3, 100 MHz): δ (C=O), 80.0 (CMe 3 ), 71.7 (C alkyne ), 30.0 (CH 2 N), 28.1 (CH 3 Boc ). S3

4 124.1 (C trz H), 79.9 (CMe 3 ), 36.5 (CH 2 N), 28.6 (CH 3 Boc ), 21.3, 17.4 (2 Ar CH 3 ). Anal. Calcd for C 17 H 24 N 4 O 2 (316.39): C, 64.53; H, 7.65; N, Found: C, 64.32; H, 7.53; N, General procedure for the synthesis of the triazolium iodides 1a-h To a MeCN solution of triazole was added MeI and the mixture was stirred under microwave irradiation at 90 C for 5 h. All volatiles were then removed in vacuo. The residue was washed with copious amounts of Et 2 O several times and dried in vacuo to afford the crude triazolium salt 1. Microanalytically pure samples were obtained by recrystallization from hot acetone. 1-(3,4,5,-Trimethoxyphenyl)-3-methyl-4-(4-methoxyphenyl)-1,2,3-triazolium iodide 1b. Reaction of 1-(3,4,5,-trimethoxyphenyl)-4-(4-methoxyphenyl)-1,2,3-triazole (700 mg, 2.0 mmol) and CH 3 I (1.48 g, 10.3 mmol) in MeCN (10 ml) according to the general procedure afforded 1b as a pale yellow powder (940 mg, 95%). 1 H NMR (CDCl 3, 500 MHz): δ (s, 1H, H trz ), 7.95 (d, 3 J HH = 7.2 Hz, 2H Ar ), 7.38 (s, 2H Ar ), 6.91 (d, 3 J HH = 7.2 Hz, 2H Ar ), 4.45 (s, 3H, NCH 3 ), 4.04 (s, 6H, OCH 3 ), 3.92 (s, 3H, OCH 3 ), 3.76 (s, 3H, OCH 3 ). 13 C{ 1 H} NMR (CDCl 3, 125 MHz): δ 162.5, (2 C Ar ), (C trz Ar), 140.8, 131.8, (3 C Ar ), (C trz -H), 115.1, 113.2, 99.3 (3 C Ar ), 61.2 (OCH 3 ), 58.1 (OCH 3 ), 55.7 (OCH 3 ), 40.1 (NCH 3 ). Anal. Calcd for C 19 H 22 IN 3 H 2 O (501.32): C, 45.52; H, 4.83; N, Found: C, 45.99; H, 4.35; N, ,4-Di-tert-butyl-3-methyl-1,2,3-triazolium iodide 1d. Reaction of 1,4-di-tert-butyl-1,2,3- triazole (282 mg, 1.5 mmol) and CH 3 I (2.23 g, mmol) in MeCN (10 ml) according to the general procedure afforded 1d as a white powder (462 mg, 92%). 1 H NMR (CDCl 3, 500 MHz): δ 8.89 (s, 1H, H trz ), 4.40 (s, 3H, NCH 3 ), 1.88, 1.61 (2 (s, 9H C-CH 3 ). 13 C{ 1 H} NMR (CDCl 3, 125 MHz): δ (C trz tbu), (C trz -H), 67.1 (N-CMe 3 ), 41.2 (NCH 3 ), 31.9 (C-CMe 3 ), 29.9, 29.4 (2 C-CH 3 ). Anal. Calcd for C 11 H 22 IN 3 (323.08): C, 40.88; H, 6.86; N, Found: C, 40.65; H, 6.65; N, Adamantyl-3-methyl-4-phenyl-1,2,3-triazolium iodide 1e. Reaction of 1-adamantyl-4- phenyl-1,2,3-triazole (200 mg, 0.7 mmol) and CH 3 I (524 mg, 3.69 mmol) in a mixture of MeCN/DCM (5: 5 ml) according to the general procedure afforded 1e as a white powder (150 mg, 50%). 1 H NMR (CDCl 3, 500 MHz): δ 9.10 (s, 1H, H trz ), 7.87 (d, 3 J HH = 9.5 Hz, 2H Ar ), 7.56 S4

5 (m, 3H Ar ), 4.33 (s, 3H, NCH 3 ), 2.46 (m, 6H, CH 2 ada ), 2.34 (bs, 3H, CH ada ), 1.81 (m, 6H, CH 2 ada ). 13 C{ 1 H} NMR (CDCl 3, 125 MHz): δ (C trz Ph), (C Ph ), (C Ph ), (C Ph ), (C trz -H), (C Ph ), 67.2 (C ada -N), 42.4 (CH 2 ada ), 39.6 (NCH 3 ), 35.4 (CH 2 ada ), 29.7 (CH ada ). Anal. Calcd for C 19 H 24 IN 3 (421.32): C, 54.16; H, 5.74; N, Found: C, 53.75; H, 5.75; N, Adamantyl-3-methyl-4-tert-butyl-1,2,3-triazolium iodide 1f. Reaction of 1-adamantyl-4- tert-butyl-1,2,3-triazole (400 mg, 1.5 mmol) and CH 3 I (2186 mg, 15.4 mmol) in a mixture of MeCN/DCM (5: 5 ml) according to the general procedure afforded 1f as a white powder (500 mg, 80%). 1 H NMR (CDCl 3, 500 MHz): δ 8.87 (s, 1H, H trz ), 4.40 (s, 3H, NCH 3 ), 2.42 (m, 6H, CH 2 ada ), 2.34 (bs, 3H, CH ada ), 1.81 (m, 6H, CH 2 ada ), 1.60 (s, 9H, C-CH 3 ). 13 C{ 1 H} NMR (CDCl 3, 125 MHz): δ (C trz tbu), (C trz -H), 67.1 (C ada -N), 42.2 (CH 2 ada ), 41.1 (NCH 3 ), 35.4 (CH 2 ada ), 31.9 (C-CMe 3 ), 29.7 (CH ada ), 29.4 (C-CH 3 ). Anal. Calcd for C 17 H 28 IN 3 (401.33): C, 50.88; H, 7.03; N, Found: C, 50.77; H, 7.05; N, Mesityl-3-methyl-4-tert-butyl-methylcarbamate-1,2,3-triazolium triflate 1h. MeOTf (645 mg, 3.9 mmol) was added dropwise to a solution of 1-mesityl-4-tert-butyl-methylcarbamate- 1,2,3-triazole (1.0 g, 3.9 mmol) in Et 2 O (100 ml). After stirring at RT for 16 h, the formed white solid was collected by filtration, washed with pentane (2 50 ml), and dried in vacuo to afford triazolium species 1h as the triflate salt (1.22 g, 80%). 1 H NMR (CDCl 3, 400 MHz) δ 8.45 (s, 1H, H trz ) 7.03 (s, 2H, H Ar ), 6.55 (t, 3 J HH = 5.6 Hz, 1H, NH), 4.68 (d, 3 J HH = 5.6 Hz, 2H, CH 2 N), 4.49 (NCH 3 ), 2.37 (s, 3H, Ar CH 3 ), 2.02 (s, 6H, Ar CH 3 ), 1.40 (s, 9H, CH 3 Boc ). 13 C{1H} NMR (CDCl 3, 100 MHz): (N C=O), (C trz alkyl), 142.8, (2 C Mes ), (C trz H), 131.4, (2 C Mes ), (q, 1 J CF = 320 Hz, CF 3 SO 3 ), 80.6 (CMe 3 ), 38.9 (NCH 3 ), 34.1 (CH 2 N), 28.4 (CH 3 Boc ), 21.4, 17.3 (2 Ar CH 3 ). Anal. Calcd for C 19 H 27 F 3 N 4 SO 5 (480.50) H 2 O: C, 45.78; H, 5.86; N, Found: C, 45.74; H, 5.31; N, Mesityl-3-methyl-4-tert-butyl-methylcarbamate-1,2,3-triazolium chloride 1h. The triazolium triflate 1h (1.22 g, 2.53 mmol) was dissolved in 5 ml of MeOH and eluted over 8 h through an ion exchange column (Dowex mesh Cl form). The volatiles were removed in vacuo to afford the product a yellow oil which was recrystallized from CH 2 Cl 2 S5

6 /pentane and then dried in vacuo, yielding 1h as a white hygroscopic solid (500 mg, 54%). 1 H NMR (CDCl 3, 400 MHz) δ 8.89 (s, 1H, H trz ), 7.56 (t, 3 J HH = 5.6 Hz, 1H, NH), 7.02 (s, 2H, H Ar ), 4.83 (d, 3 J HH = 5.6 Hz, 2H, CH 2 N), 4.61 (NCH 3 ), 2.36 (s, 3H, Ar CH 3 ), 2.03 (s, 6H, Ar CH 3 ), 1.38 (s, 9H, CH 3 Boc ). 13 C{1H} NMR (CDCl 3, 100 MHz): (N C=O), (C trz alkyl), 142.7, (2 C Mes ), (C trz H), 131.4, (2 C Mes ), 80.3 (CMe 3 ), 39.4 (NCH 3 ), 34.2 (CH 2 N), 28.4 (CH 3 Boc ), 21.4, 17.5 (2 Ar CH 3 ). Anal. Calcd for C 18 H 27 ClN 4 O 2 (366.88): C, 58.93; H, 7.42; N, Found: C, 58.45; H, 7.32; N, S6

7 2. Dynamic light scattering results Dynamic light scattering was performed on a Malvern Zetasizer ZS90 using a 633 nm laser and non-invasive backscatter optics. Figure S1 Size distribution (DLS) of particles upon catalytic runs using benzaldehyde, isocyanoacetate, NEtiPr 2, AgBF 4 and complex 2a (cf. Table 4, entry 1): a) measurement after 10 min (44% conversion); b) after 30 min (95% conversion); c) after 90 min. S7

8 3. Time-conversion profile for complexes 2b and 2d Figure S2 Representative time-conversion profiles of 2b and 2d with 0.5 mol% catalyst loading. 3. Crystallographic details Table S1 Crystal data and structure refinement for 2a. CCDC No Empirical formula C 21 H 25 AuClN 3 Formula weight Å Monoclinic Space group P2 1 /n (#14) Unit cell dimensions a = (2) Å b = (3) Å β= (2) c = (4) Å Volume (9) Å 3 Z 4 Density (calculated) Mg m 3 Absorption coefficient mm 1 F(000) 1072 Crystal size x x mm 3 Theta range for data collection 3.19 to <=h<=8, 21<=k<=21, 28<=l<=28 S8

9 Reflections collected Independent reflections 5107 [R(int) = ] Completeness to θ = % Max. and min. transmission and Data / restraints / parameters 5107 / 0 / 242 Goodness of fit on F Final R indices [I>2σ(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e Å 3 Table S2 Crystal data and structure refinement for 2b. CCDC No Empirical formula C 19 H 21 AuClN 3 O 4 Formula weight Å Triclinic Space group P 1 (#2) Unit cell dimensions a = (3) Å b = (4) Å β= (3) c = (5) Å Volume (12) Å 3 Z 4 Density (calculated) Mg m 3 Absorption coefficient mm 1 F(000) 1136 Crystal size x x mm 3 Theta range for data collection 2.94 to Reflections collected Independent reflections 9775 [R(int) = ] Completeness to θ = % 15<=h<=15, 18<=k<=17, 19<=l<=19 Max. and min. transmission and Data / restraints / parameters 9775 / 0 / 515 Goodness of fit on F Final R indices [I>2σ(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e Å 3 S9

10 Table S3 Crystal data and structure refinement for 2d. CCDC No Empirical formula C 11 H 21 AuClN Formula weight Å Monoclinic Space group P2 1 /n (#14) Unit cell dimensions a = (1) Å b = (7) Å β= (1) c = (2) Å Volume (2) Å 3 Z 4 Density (calculated) Mg m 3 Absorption coefficient mm 1 F(000) 816 Crystal size x x mm 3 Theta range for data collection 4.37 to Reflections collected a) Independent reflections 3546 [R(int) = a) ] Completeness to θ = % 14<=h<=14, 8<=k<=8, 22<=l<=21 Max. and min. transmission and Data / restraints / parameters 3546 / 0 / 153 Goodness of fit on F Final R indices [I>2σ(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e Å 3 a) The crystal was a non merohedral twin. Symmetry equivalent reflections were merged during data reduction for the HKLF5 file. The R int and the number of collected reflections were taken from an HKLF4 file and are thus approximations. Table S4 Crystal data and structure refinement for 2e. CCDC No Empirical formula C 19 H 23 AuClN 3 Formula weight Å Monoclinic Space group P2 1 /c (#14) S10

11 Unit cell dimensions a = (2) Å b = (3) Å β= (2) c = (2) Å Volume (6) Å 3 Z 4 Density (calculated) Mg m 3 Absorption coefficient mm 1 F(000) 1016 Crystal size x x mm 3 Theta range for data collection 3.05 to <=h<=14, 24<=k<=23, 13<=l<=13 Reflections collected Independent reflections 4806 [R(int) = ] Completeness to θ = % Max. and min. transmission and Data / restraints / parameters 4806 / 0 / 218 Goodness of fit on F Final R indices [I>2σ(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e Å 3 Table S5 Crystal data and structure refinement for 2h. CCDC No Empirical formula C 36 H 50 Au 2 N 8 O 4 CHCl 3 Formula weight Å Monoclinic Space group C2/c (#15) Unit cell dimensions a = (3) Å b = (3) Å β= (9) c = (2) Å Volume (7) Å 3 Z 4 Density (calculated) Mg m 3 Absorption coefficient mm 1 F(000) 2280 Crystal size x x mm 3 Theta range for data collection 3.47 to Reflections collected Independent reflections 4501 [R(int) = ] 36<=h<=36, 7<=k<=7, 34<=l<=34 S11

12 Completeness to θ = % Max. and min. transmission and Data / restraints / parameters 4501 / 0 / 257 Goodness of fit on F Final R indices [I>2σ(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e Å 3 Table S6 Crystal data and structure refinement for 3 CCDC No Empirical formula C 39 H 40 AuBF 4 N 3 P Formula weight Å Triclinic Space group P 1 (#2) Unit cell dimensions a = (3) Å α= (2) b = (3) Å β= (2) c = (4) Å γ = (2) Volume (13) Å 3 Z 4 Density (calculated) Mg m 3 Absorption coefficient mm 1 F(000) 1720 Crystal size x x mm 3 Theta range for data collection 2.92 to <=h<=19, 19<=k<=19, 24<=l<=24 Reflections collected Independent reflections [R(int) = ] Completeness to θ = % Max. and min. transmission and Data / restraints / parameters / 26 / 936 a) Goodness of fit on F Final R indices [I>2σ(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e Å 3 a) The two disorder parts were restrained to have the same shape using SADI. DELU restraints were applied to all disordered atoms. S12

13 Table S7 Crystal data and structure refinement for 4e. CCDC No Empirical formula [C 38 H 46 N 6 Au] 4 [Cl 2 I] 1.58 [Cl] 2.42 C 4 H 10 O 0.83 H 2 O a) Formula weight Å Monoclinic Space group C2 (#5) Unit cell dimensions a = (3) Å b = (1) Å β= (1) c = (2) Å Volume (13) Å 3 Z 2 Density (calculated) Mg m 3 Absorption coefficient mm 1 F(000) Crystal size x x mm 3 Theta range 2.82 to Reflections collected Independent reflections [R(int) = ] Completeness to θ = % 44<=h<=41, 22<=k<=22, 23<=l<=23 Max. and min. transmission and Data / restraints / parameters / 7 / 910 b) Goodness of fit on F Final R indices [I>2σ(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter 0.031(3) Largest diff. peak and hole and e Å 3 a) The hydrogen atoms of the water molecule could not be detected. b) The oxygen atom of the water molecule was restrained to have a roughly spherical thermal ellipsoid using ISOR. Table S8 Crystal data and structure refinement for 6. CCDC No Empirical formula C 42 H 48 BN 4 F 4 Au Formula weight Å Orthorhombic Space group Pnna (#52) S13

14 Unit cell dimensions a = (2) Å b = (3) Å c = (1) Å Volume (14) Å 3 Z 8 Density (calculated) Mg m 3 Absorption coefficient mm 1 F(000) 3584 Crystal size x x mm 3 Theta range for data collection 2.93 to <=h<=21, 42<=k<=42, 21<=l<=21 Reflections collected Independent reflections [R(int) = ] Completeness to θ = % Max. and min. transmission and Data / restraints / parameters / 0 / 484 Goodness of fit on F Final R indices [I>2σ(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e Å 3 S14