A Highly Active Gold(I)-Silver(I) Oxo Cluster Activating sp 3 C-H. Bonds of Methyl Ketones under Mild Conditions

Transcription

1 Supporting information A Highly Active Gold(I)-Silver(I) Oxo Cluster Activating sp 3 C-H Bonds of Methyl Ketones under Mild Conditions Xiao-Li Pei, Yang Yang, Zhen Lei, Shan-Shan Chang, Zong-Jie Guan, Xian-Kai Wan, Ting-Bin Wen, and Quan-Ming Wang* State Key Lab of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (ichem), Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen , Fujian, P. R. China qmwang@xmu.edu.cn S1

2 Contents I. Synthesis II. Characterization Figure S1. 1 H NMR (500.2 MHz) spectrum of 3 in CD 3 CN Figure S2. 31 P NMR (162 MHz) spectrum of 3 in CD 3 CN Figure S3. 13 C NMR (125.8 MHz) spectrum of 3 in CD 3 CN Figure S4. 1 H NMR (400.1 MHz) spectrum of 2a in CD 3 CN Figure S5. 31 P NMR (162 MHz) spectrum of 2a in CD 3 CN Figure S6. 13 C NMR (100.6 MHz) spectrum of 2a in CD 3 CN Figure S7. HSQC spectrum of 2a in CD 3 CN Figure S8. 1 H- 1 H-COSY spectrum of 2a in CD 3 CN Figure S9. 1 H NMR (400.1 MHz) spectrum of 2b in CD 3 CN Figure S P NMR (162 MHz) spectrum of 2b in CD 3 CN Figure S C NMR (100.6 MHz) spectrum of 2b in CD 3 CN Figure S12. 1 H NMR (500.2 MHz) spectrum of 2c in CD 3 CN Figure S P NMR (202.5 MHz) spectrum of 2c in CD 3 CN Figure S C NMR (125.8 MHz) spectrum of 2c in CD 3 CN Figure S15. 1 H NMR (400.1 MHz) spectrum of 2d in CD 3 CN Figure S P NMR (162 MHz) spectrum of 2d in CD 3 CN Figure S C NMR (150.9 MHz) spectrum of 2d in CD 3 CN Figure S18. 1 H NMR (600.1 MHz) spectrum of 2e in CD 3 CN Figure S P NMR (202.5 MHz) spectrum of 2e in CD 3 CN Figure S C NMR (150.9 MHz) spectrum of 2e in CD 3 CN Figure S21. 1 H NMR (400.1 MHz) spectrum of 2f in CD 3 CN Figure S P NMR (162 MHz) spectrum of 2f in CD 3 CN Figure S C NMR (100.6 MHz) spectrum of 2f in CD 3 CN Figure S24. 1 H NMR (400.1 MHz) spectrum of 2g in CD 3 CN Figure S P NMR (162 MHz) spectrum of 2g in CD 3 CN Figure S C NMR (150.9 MHz) spectrum of 2g in CD 3 CN Figure S27. 1 H NMR (500.2 MHz) spectrum of 2h in CD 3 CN Figure S P NMR (202.5 MHz) spectrum of 2h in CD 3 CN Figure S C NMR (150.9 MHz) spectrum of 2h in CD 3 CN Figure S30. 1 H NMR (500.2 MHz) spectrum of 2i in CD 3 CN Figure S P NMR (202.5 MHz) spectrum of 2i in CD 3 CN Figure S C NMR (150.9 MHz) spectrum of 2i in CD 3 CN Figure S33. 1 H- 1 H-COSY spectrum of 2i in CD 3 CN Figure S34. 1 H NMR (500.2 MHz) spectrum of 2j in CD 3 CN Figure S P NMR (202.5 MHz) spectrum of 2j in CD 3 CN Figure S C NMR (125.8 MHz) spectrum of 2j in CD 3 CN Figure S37. 1 H- 1 H-COSY spectrum of 2j in CD 3 CN Figure S38. The EDX analysis of complex 1 Figure S39. MS spectra of complex 5. The observed isotopic pattern of [(CH 2 CHCOCH 2 CH 2 )Au 2 (PC 6 H 5 C 10 H 8 N 2 ) 2 ] + (black line) at peak is perfectly in agreement with the simulated one (red line). S2

3 I. Synthesis [OAu 3 Ag(PPhpy 2 ) 3 ](BF 4 ) 2 (3) To a solution of Au(Me 2 S)Cl (246.4 mg, 0.84 mmol) in dichloromethane (10 ml) were added PPhpy 2 (220.9 mg, 0.84 mmol). The solution was stirred for 20 min, and the solvent was then removed under reduced pressure. The resulting solid was dissolved in 10 ml CH 3 OH, freshly prepared Ag 2 O (389.8 mg, 1.68 mmol) and NaBF 4 (526.7 mg, 4.8 mmol) were added. After 2h stirring, CH 3 OH was removed, and the crude product was extracted with dichloromethane (10 ml 3). The extract was concentrated to ca. 5 ml, and 5 ml Et 2 O was layered on for diffusion, which gave the product as gray block-like crystals after a day. Yield: mg (62.4%, based on gold). 1 H NMR (500.2 MHz, CD 3 CN, ppm): δ 8.16 (d, 6H, py), (m, 6H, py), (m, 6 + 6H, Ph + py), (m, 3H, Ph), (m, 6H, py), (m, 6H, Ph). 31 P NMR (162 MHz, CD 3 CN, ppm): C NMR (125.8 MHz, CD 3 CN, ppm): (d, J CP = 17.61, py), (d, J CP = 90.58, py), (d, J CP = 8.81, py), (d, J CP = 13.84, py), (s, Ph), (d, J CP = 22.64, Ph), (d, J CP = 12.58, py), (s, Ph), (d, J CP = 61.64, Ph). IR (KBr, cm -1 ): v 1084 (br, B-F). Anal. Calcd for C 48 H 39 B 2 N 6 OF 8 P 3 AgAu 3 : C, 34.29; H, 2.34; N, Found: C, 33.82; H, 2.44; N, [OAu 3 Ag 3 (PPhpy 2 ) 3 ](BF 4 ) 4 (1) [O(AuPPhpy 2 ) 3 Ag](BF 4 ) 2 (3) (67.5 mg, mmol) was suspending in methanol (2 ml), solution of 2 equiv. AgBF 4 in methanol was added, then the mixture was stirred for 30 min at room temperature. After completion, the resulting suspension was isolated by centrifugal sedimentation and milky solid was obtained as complex 1, yield 77.4 mg (93.5%, based on gold). The EDX analysis of complex 1: elemental composition of the sample (at. %) Au, 49.35; Ag, Anal. Calcd for C 48 H 39 B 4 N 6 OF 16 P 3 Ag 3 Au 3 : C, 27.84; H, 1.90; N, Found: C, 28.14; H, 2.23; N, As 1 is poorly soluble in CH 2 Cl 2 and highly reactive in soluble solvent such as CH 3 CN, acetone and DMSO, NMR data were not available. [OAu 3 Ag 3 (PPh(5-Mepy) 2 ) 3 ](BF 4 ) 4 (4) The synthesis route of 4 is similar to [OAu 3 Ag 3 (PPhpy 2 ) 3 ](BF 4 ) 4 (1). The phosphine ligand is PPh(5-Mepy) 2 instead. The corresponding product 4 can be redissolved in dichloromethane, and the solution was layered by 5 ml Et 2 O for diffusion, colorless block crystal was obtained as 4. Anal. Calcd for C 54 H 51 B 4 N 6 OF 16 P 3 Ag 3 Au 3 : C, 30.10; H, 2.39 ; N, Found: C, 30.55; H, 2.40; N, The same reason as for 1, NMR data were not available. [(CH 2 CHCOCH 2 CH 2 )Au 2 (PC 6 H 5 C 10 H 8 N 2 ) 2 ](BF 4 ) (5) Mixing 3 (60 mg, mmol) with 2 equiv. AgBF 4 in methanol (2 ml), and then adding excess cyclopentanone (500 μl). The mixture was stirred at room temperature for 12 h to give a brown solution, the resulting solution was evaporated to about 0.5 ml, and then was precipitated by adding excess Et 2 O. Finally brown solid was S3

4 collected by centrifugation (37.4 mg). Unfortunately, this crude product was a mixture, and the purification was not successful, which prevented from further characterization. Dissolving small amount of this crude product in MeOH to conduct MS measurement, showing the dominant peak at : [(CH 2 CHCOCH 2 CH 2 )Au 2 (PC 6 H 5 C 10 H 8 N 2 ) 2 ] +. See Figure S39. II. Characterization [H 3 CCOCAu 4 Ag 4 (PPhpy 2 ) 4 ](BF 4 ) 5 (2a) 1 H NMR (400.1 MHz, CD 3 CN, ppm): δ8.36 (s, 8H, py), (m, 8H, py), (q, 8H, Ph), 7.49 (s, 8H, py), (m, H, Ph + py), 2.92 (s, 3H, CH 3 ). 31 P NMR (162 MHz, CD 3 CN, ppm): (s). 13 C NMR (100.6 MHz, CD 3 CN, ppm): (s, C=O), δ (d, J CP = 18.11, C=N, py), (d, J CP = 81.49, C ispo, py), (s, C meta, py), (d, J CP = 15.10, C ortho, Ph), (s, C para, Ph), (d, J CP = 17.50, C ortho, py), (d, J CP = 11.87, C meta, Ph), (s, C para, py), (d, J CP = 53.82, C ispo, Ph), 37.04(s, CH 3 ). The signal of the carbon connected to gold atom was not detected in 13 C NMR spectrum even after prolonged accumulation. IR (KBr, cm -1 ): v 1084(br, B-F). Anal. Calcd for C 67 H 55 B 5 N 8 OF 20 P 4 Ag 4 Au 4 : C, 29.10; H, 2.00; N, Found: C, 29.39; H, 2.35; N, [PhCOCAu 4 Ag 4 (PPhpy 2 ) 4 ](BF 4 ) 5 (2b) 1 H NMR (400.1 MHz, CD 3 CN, ppm): δ8.48 (d, 2H, PhCO), 8.39 (m, 8H, py), (t, 8H, py), (q, 8H, Ph), 7.44 (m, 8H, py), (m, 20H+3H, Ph + py + PhCO), 2.81 (s, 3H, CH 3 ). 31 P NMR (162 MHz, CD 3 CN, ppm): 37.47(s). 13 C NMR (100.6 MHz, CD 3 CN, ppm): δ (s, C=O), (d, J CP = 18.11, C=N, py), (d, J CP = 81.49, C ispo, py), (d, J CP = 4.02, C meta, py), (d, J CP = 14.08, C ortho, Ph), (s, C para, Ph), (s, C ispo, PhCO), (d, J CP = 19.11, C ortho, py), (d, J CP = 12.07, C meta, Ph), (s, C para, PhCO), (s, C meta + C ortho, PhCO), (s, C para, py), (d, J CP = 54.32, C ispo, Ph). The signal of the carbon connected to gold atom was not detected in 13 C NMR spectrum even after prolonged accumulation. IR (KBr, cm -1 ): v 1084 (br, B-F). Anal. Calcd for C 72 H 57 B 5 N 8 OF 20 P 4 Ag 4 Au 4 : C, 30.58; H, 2.03; N, Found: C, 30.41; H, 2.34; N, [o-ch 3 PhCOCAu 4 Ag 4 (PPhpy 2 ) 4 ](BF 4 ) 5 (2c) 1 H NMR (500.2 MHz, CD 3 CN, ppm): δ8.38 (d, 8H, py), 8.22 (d, 1H, PhCO), 7.88 (m, 8H, py), 7.60 (q, 8H, Ph), 7.47 (m, 8H, py), (m, H, Ph + py), (m, 2H, PhCO), 6.95 (m, 1H, PhCO), 2.42 (s, 3H, CH 3 ). 31 P NMR (202.5 MHz, CD 3 CN, ppm): 37.57(s). 13 C NMR (125.8 MHz, CD 3 CN, ppm): δ (s, C=O), (d, J CP = 17.6, C=N, py), (d, J CP = 80.51, C ispo, py), (s, PhCO), (s, C meta, py), (d, J CP = 15.10, C ortho, Ph), (s, C para, Ph), (s, PhCO), (s, PhCO), (d, J CP = 18.75, C ortho, py), (d, J CP = 12.58, C meta, Ph), (s, PhCO), (s, C para, py), (s, PhCO), (d, J CP = 51.58, C ispo, Ph) (s, PhCO), (s, CH 3 ). The signal of the carbon S4

5 connected to gold atom was not detected in 13 C NMR spectrum even after prolonged accumulation. IR (KBr, cm -1 ): v 1083 (br, B-F). Anal. Calcd for C 73 H 59 B 5 N 8 OF 20 P 4 Ag 4 Au 4 : C, 30.86; H, 2.09; N, Found: C, 30.52; H, 2.23; N, [o-nh 2 PhCOCAu 4 Ag 4 (PPhpy 2 ) 4 ](BF 4 ) 5 (2d) 1 H NMR (400.1 MHz, CD 3 CN, ppm): δ8.42 (s, 8H, py), 7.97(s, 1H, PhCO), 7.88(m, 8H, py), 7.58 (s, 8H, Ph), 7.45 (s, 8H, py), (m, H, Ph + py), 6.94 (m, 2H, PhCO), 6.57 (m, 1H, PhCO), 4.99(s, 2H, NH 2 ). 31 P NMR (162 MHz, CD 3 CN, ppm): 37.25(s). 13 C NMR (150.9 MHz, CD 3 CN, ppm): δ (s, C=O), (d, J CP = 18.11, C=N, py), (d, J CP = 79.98, C ispo, py), (s, PhCO), (s, C meta, py), (s, PhCO), (d, J CP = 15.09, C ortho, Ph), (s, C para, Ph), (d, J CP = 18.11, C ortho, py), (s, PhCO), (d, J CP = 10.56, C meta, Ph), (s, C para, py), (d, J CP = 54.32, C ispo, Ph) (s, PhCO), (s, PhCO), (s, PhCO). The signal of the carbon connected to gold atom was not detected in 13 C NMR spectrum even after prolonged accumulation. IR (KBr, cm -1 ): v 1083 (br, B-F). Anal. Calcd for C 72 H 58 B 5 N 9 OF 20 P 4 Ag 4 Au 4 : C, 30.42; H, 2.06; N, Found: C, 30.21; H, 2.20; N, [o-hophcocau 4 Ag 4 (PPhpy 2 ) 4 ](BF 4 ) 5 (2e) 1 H NMR (600.1 MHz, CD 3 CN, ppm): δ12.78 (s, 1H, O-H O), 9.74 (d, 1H, PhCO), 8.40 (s, 8H, py), (m, 8H, py), (q, 8H, Ph), 7.45 (m, 8H, py), (m, 4 + 1H, Ph + PhCO), (m, 8H, py), (m, 8H, Ph), (m, 2H, PhCO). 31 P NMR (202.5 MHz, CD 3 CN, ppm): 36.56(s). 13 C NMR (150.9 MHz, CD 3 CN, ppm): δ (s, C=O), (s, PhCO), (d, J CP = 18.11, C=N, py), (d, J CP = 81.49, C ispo, py), (s, C meta, py), (s, PhCO), (d, J CP = 15.09, C ortho, Ph), (s, PhCO), (s, C para, Ph), (d, J CP = 18.11, C ortho, py), (d, J CP = 12.07, C meta, Ph), (s, C para, py), (d, J CP = 54.32, C ispo, Ph) (s, PhCO), (s, PhCO), (s, PhCO). The signal of the carbon connected to gold atom was not detected in 13 C NMR spectrum even after prolonged accumulation. IR (KBr, cm -1 ): v 1084 (br, B-F). Anal. Calcd for C 72 H 57 B 5 N 8 O 2 F 20 P 4 Ag 4 Au 4 : C, 30.41; H, 2.02; N, Found: C, 30.52; H, 2.16; N, [2-pyCOCAu 4 Ag 4 (PPhpy 2 ) 4 ](BF 4 ) 5 (2f) 1 H NMR (400.1 MHz, CD 3 CN, ppm): δ8.66 (d, 1H, pyco), 8.33(s, 8H, py), 8.24 (d, 1H, pyco), 8.12 (t, 1H, pyco), 7.98(d, 1H, pyco), (m, 8H, py), (m, 36H, py+ph). 31 P NMR (162 MHz, CD 3 CN, ppm): 38.00(s). 13 C NMR (100.6 MHz, CD 3 CN, ppm): δ (s, C=O), (s, pyco), (d, J CP = 18.11, C=N, py), (d, J CP = 79.47, C ispo, py), (s, pyco), (s, pyco), (s, C meta, py), (d, J CP = 15.09, C ortho, Ph), (s, C para, Ph), (d, J CP = 17.10, C ortho, py), (d, J CP = 12.07, C meta, Ph), (s, pyco), (s, C para, py), (d, J CP = 52.31, C ispo, Ph), (s, pyco). The signal of the carbon connected to gold atom was not detected in 13 C NMR spectrum even after S5

6 prolonged accumulation. IR (KBr, cm -1 ): v 1084 (br, B-F). Anal. Calcd for C 71 H 56 B 5 N 9 OF 20 P 4 Ag 4 Au 4 : C, 30.15; H, 2.00; N, Found: C, 30.32; H, 2.23; N, [2-thiazolylCOCAu 4 Ag 4 (PPhpy 2 ) 4 ](BF 4 ) 5 (2g) 1 H NMR (400.1 MHz MHz, CD 3 CN, ppm): δ9.40 (s, 1H, thiazolyl), 8.81(d, 1H, thiazolyl), 8.36 (d, 8H, py), 7.86 (m, 8H, py), (q, 8H, Ph), (m, 8+12H, py+ph ), (m, 8H, py). 31 P NMR (162 MHz, CD 3 CN, ppm): 37.27(s). 13 C NMR (150.9 MHz, CD 3 CN, ppm): δ (s, C=O), (s, SC=N, thiazoyl), (d, J CP = 18.11, C=N, py), (d, J CP = 83.00, C ispo, py), (s, HC-N, thiazoyl), (s, C meta, py), (d, J CP = 15.09, C ortho, Ph), (s, C para, Ph), (d, J CP = 16.60, C ortho, py), (d, J CP = 12.07, C meta, Ph), (s, HC-S, thiazoyl), (s, C para, py), (d, J CP = 54.32, C ispo, Ph). The signal of the carbon connected to gold atom was not detected in 13 C NMR spectrum even after prolonged accumulation. IR (KBr, cm -1 ): v 1083 (br, B-F). Anal. Calcd for C 69 H 54 B 5 N 9 OF 20 SP 4 Ag 4 Au 4 : C, 29.24; H, 1.92; N, Found: C, 29.07; H, 2.03; N, [ t- butylcocau 4 Ag 4 (PPhpy 2 ) 4 ](BF 4 ) 5 (2h) 1 H NMR (500.2 MHz, CD 3 CN, ppm): δ8.41 (s, 8H, py), 7.90 (m, 8H, py), (m, 8H, Ph), 7.48 (s, 8H, py ), (m, H, Ph + py), 1.59 (m, 9H, t- Bu). 31 P NMR (202.5 MHz, CD 3 CN, ppm): 37.48(s). 13 C NMR (150.9 MHz, CD 3 CN, ppm): δ (s, C=O), (d, J CP = 18.11, C=N, py), (d, J CP = 79.98, C ispo, py), (d, J CP = 4.53, C meta, py), (d, J CP = 13.58, C ortho, Ph), (s, C para, Ph), (d, J CP = 18.11, C ortho, py), (d, J CP = 12.07, C meta, Ph), (s, C para, py), (d, J CP = 52.82, C ispo, Ph), (s, C ), (s, CH 3 ). The signal of the carbon connected to gold atom was not detected in 13 C NMR spectrum even after prolonged accumulation. IR (KBr, cm -1 ): v 1083 (br, B-F). IR (KBr, cm -1 ): v 1083 (br, B-F). Anal. Calcd for C 70 H 61 B 5 N 8 OF 20 P 4 Ag 4 Au 4 : C, 29.95; H, 2.19; N, Found: C, 30.15; H, 2.37; N, [CH 3 CH 2 COCAu 4 Ag 4 (PPhpy 2 ) 4 ](BF 4 ) 5 (2i) 1 H NMR (500.2 MHz, CD 3 CN, ppm): δ8.40 (s, 8H, py), (t, 8H, py), (q, 8H, Ph), 7.48 (s, 8H, py ), (m, 4 + 8H, Ph + py), (t, 8H, Ph), (q, 2H, CH 2 ), (t, 3H, CH 3 ). 31 P NMR (202.5 MHz, CD 3 CN, ppm): 37.58(s). 13 C NMR (150.9 MHz, CD 3 CN, ppm): δ (s, C=O), (d, J CP = 16.60, C=N, py), (d, J CP = 79.98, C ispo, py), (s, C meta, py), (d, J CP = 15.09, C ortho, Ph), (s, C para, Ph), (d, J CP = 18.11, C ortho, py), (d, J CP = 10.56, C meta, Ph), (s, C para, py), (d, J CP = 52.82, C ispo, Ph), (s, CH 2 ), (s, CH 3 ). The signal of the carbon connected to gold atom was not detected in 13 C NMR spectrum even after prolonged accumulation. IR (KBr, cm -1 ): v 1084 (br, B-F). Anal. Calcd for C 68 H 57 B 5 N 8 OF 20 P 4 Ag 4 Au 4 : C, 29.38; H, 2.07; N, Found: C, 29.31; H, 2.36; N, S6

7 [ i- PrCOCAu 4 Ag 4 (PPhpy 2 ) 4 ](BF 4 ) 5 (2j) 1 H NMR (500.2 MHz, CD 3 CN, ppm): δ8.36 (s, 8H, py), 7.90 (m, 8H, py), (m, 8H, Ph), 7.47 (s, 8H, py ), (m, 4 + 8H, Ph + py), (m, 8H, Ph), (t, 1H, CH), (d, 6H, CH 3 ). 31 P NMR (202.5 MHz, CD 3 CN, ppm): 37.73(s). 13 C NMR (125.8 MHz, CD 3 CN, ppm): δ (s, C=O), (d, J CP = 17.62, C=N, py), (d, J CP = 80.51, C ispo, py), (s, C meta, py), (d, J CP = 13.84, C ortho, Ph), (s, C para, Ph), (d, J CP = 17.61, C ortho, py), (d, J CP = 11.32, C meta, Ph), (s, C para, py), (d, J CP = 54.09, C ispo, Ph), 45.64(s, CH ), (s, CH 3 ). The signal of the carbon connected to gold atom was not detected in 13 C NMR spectrum even after prolonged accumulation. IR (KBr, cm -1 ): v 1083 (br, B-F). Anal. Calcd for C 69 H 59 B 5 N 8 OF 20 P 4 Ag 4 Au 4 : C, 29.67; H, 2.13; N, Found: C, 29.87; H, 2.36; N, Figure S1. 1 H NMR (500.2 MHz) spectrum of 3 in CD 3 CN S7

8 Figure S2. 31 P NMR (162 MHz) spectrum of 3 in CD 3 CN Figure S3. 13 C NMR (125.8 MHz) spectrum of 3 in CD 3 CN S8

9 Figure S4. 1 H NMR (400.1 MHz) spectrum of 2a in CD 3 CN Figure S5. 31 P NMR (162 MHz) spectrum of 2a in CD 3 CN S9

10 Figure S6. 13 C NMR (100.6 MHz) spectrum of 2a in CD 3 CN S10

11 Figure S7. HSQC spectrum of 2a in CD 3 CN Figure S8. 1 H- 1 H-COSY spectrum of 2a in CD 3 CN Figure S9. 1 H NMR (400.1 MHz) spectrum of 2b in CD 3 CN S11

12 Figure S P NMR (162 MHz) spectrum of 2b in CD 3 CN Figure S C NMR (100.6 MHz) spectrum of 2b in CD 3 CN S12

13 Figure S12. 1 H NMR (500.2 MHz) spectrum of 2c in CD 3 CN Figure S P NMR (202.5 MHz) spectrum of 2c in CD 3 CN S13

14 Figure S C NMR (125.8 MHz) spectrum of 2c in CD 3 CN Figure S15. 1 H NMR (400.1 MHz) spectrum of 2d in CD 3 CN S14

15 Figure S P NMR (162 MHz) spectrum of 2d in CD 3 CN Figure S C NMR (150.9 MHz) spectrum of 2d in CD 3 CN S15

16 Figure S18. 1 H NMR (600.1 MHz) spectrum of 2e in CD 3 CN Figure S P NMR (202.5 MHz) spectrum of 2e in CD 3 CN S16

17 Figure S C NMR (150.9 MHz) spectrum of 2e in CD 3 CN Figure S21. 1 H NMR (400.1 MHz) spectrum of 2f in CD 3 CN S17

18 Figure S P NMR (162 MHz) spectrum of 2f in CD 3 CN Figure S C NMR (100.6 MHz) spectrum of 2f in CD 3 CN (* stands for residual peak of 2-Acetylpyridine) S18

19 Figure S24. 1 H NMR (400.1 MHz) spectrum of 2g in CD 3 CN Figure S P NMR (162 MHz) spectrum of 2g in CD 3 CN S19

20 Figure S C NMR (150.9 MHz) spectrum of 2g in CD 3 CN Figure S27. 1 H NMR (500.2 MHz) spectrum of 2h in CD 3 CN S20

21 Figure S P NMR (202.5 MHz) spectrum of 2h in CD 3 CN Figure S C NMR (150.9 MHz) spectrum of 2h in CD 3 CN S21

22 Figure S30. 1 H NMR (500.2 MHz) spectrum of 2i in CD 3 CN Figure S P NMR (202.5 MHz) spectrum of 2i in CD 3 CN S22

23 Figure S C NMR (150.9 MHz) spectrum of 2i in CD 3 CN Figure S33. 1 H- 1 H-COSY spectrum of 2i in CD 3 CN S23

24 Figure S34. 1 H NMR (500.2 MHz) spectrum of 2j in CD 3 CN Figure S P NMR (202.5 MHz) spectrum of 2j in CD 3 CN S24

25 Figure S C NMR (125.8 MHz) spectrum of 2j in CD 3 CN Figure S37. 1 H- 1 H-COSY spectrum of 2j in CD 3 CN S25

26 Figure S38. The EDX analysis of complex 1: elemental composition of the sample (at. %) Au, 49.35; Ag, simulate m/z m/z Figure S39. MS spectra of complex 5. The observed isotopic pattern of [(CH 2 CHCOCH 2 CH 2 )Au 2 (PC 6 H 5 C 10 H 8 N 2 ) 2 ] + (black line) at peak is perfectly in agreement with the simulated one (red line). S26