Supplementary Figures

Supplementary Figures Supplementary Figure 1. DFT optimized structure of the [Ag III (L 1 )](ClO 4 ) 2 (1 ClO4 ) complex (CCDC code 978368). Hydrogen atoms and the two perchlorate anions have been omitted for clarity. Selected bond lengths [Å] and angles [º] of [Ag III (L 1 )](ClO 4 ) 2 (1 ClO4 ): Ag-C(19) 1.993, Ag-N(2) 2.122, Ag-N(6) 2.112, Ag-N(4) 2.180; C(19)-Ag-N(2) 81.43, C(19)-Ag-N(6) 81.58, N(2)-Ag-N(4) 98.94, N(6)-Ag-N(4) 98.23, C(19)-Ag-N(4) 178.23, N(2)-Ag-N(6) 161.34. 1

Supplementary Figure 2. 1 H NMR spectrum of complex [Ag III (L 1 )](ClO 4 ) 2 (1 ClO4 ) in CD 3 CN, 400 MHz, at 298 K. 2

Supplementary Figure 3. 1 H NMR{ 109 Ag} spectrum of complex [Ag III (L 1 )](ClO 4 ) 2 (1 ClO4 ) in CD 3 CN, 400 MHz, at 298 K. 3

Supplementary Figure 4. 13 C NMR spectrum of complex [Ag III (L 1 )](ClO 4 ) 2 (1 ClO4 ) in CD 3 CN, 100 MHz, at 298 K. 4

Supplementary Figure 5. 1 H 109 Ag HMBC spectrum of complex [Ag III (L 1 )](ClO 4 ) 2 (1 ClO4 ) in CD 3 CN, 400 MHz, at 298 K. 5

Supplementary Figure 6. 2D 1 H 109 Ag HSQMBC-IPAP and HSQMBC-COSY-IPAP experiments of complex [Ag III (L 1 )](ClO 4 ) 2 (1 ClO4 ) for the quantitative measurement of J( 1 H 109 Ag) coupling constants in CD 3 CN, 400 MHz, at 298 K. 6

Supplementary Figure 7. COSY spectrum of complex [Ag III (L 1 )](ClO 4 ) 2 (1 ClO4 ) in CD 3 CN, 400 MHz, at 298 K. 7

Supplementary Figure 8. NOESY spectrum of complex [Ag III (L 1 )](ClO 4 ) 2 (1 ClO4 ) in CD 3 CN, 400 MHz, at 298 K. 8

Supplementary Figure 9. 1 H 13 C HSQC spectrum of complex [Ag III (L 1 )](ClO 4 ) 2 (1 ClO4 ) in CD 3 CN, 400 MHz, at 298 K. 9

Supplementary Figure 10. HRMS (ESI-MS) spectrum of complex [Ag III (L 1 )](ClO 4 ) 2 (1 ClO4 ) in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 10

Supplementary Figure 11. 31 P-NMR of the final solution mixture of the synthesis of 2d upon addition of 3 equiv. of PPh 3 (upper spectrum). 31 P-NMR of the mixture of AgClO 4 with 3 equiv. of PPh 3 (lower spectrum). 11

Supplementary Figure 12. NMR experiment after 18 h of the addition of 0.5 equiv. of L 1 -Br showing the formation of the aryl-ag III complex 1 ClO4 in the resulting mixture of the reaction of 1 ClO4 with 1 equiv. of p-nitrophenol at 40ºC in CH 3 CN under N 2. Initial conditions: [1 ClO4 ] = 12 mm, [p-no 2 phenol] = 12 mm. After the C-O bond forming event, 0.5 equiv. of L 1 -Br added. Conditions: [1 ClO4 ] = 10.5 mm, [p-no 2 phenol] = 10.5 mm, [L 1 -Br] = 5.3 mm. (2d = C-O coupling product, intra = intramolecular C-N coupling product, 1 std = 1,3,5-trimethoxybenzene internal standard). 12

Supplementary Figure 13. UV-Vis monitoring of the formation of orange intermediate (2 ClO4 ) species upon addition of 2 equiv. of tetrabutylammonium fluoride trihydrate to complex 1 ClO4 at 25ºC in CH 3 CN under N 2. Spectrum trace a corresponds to initial complex 1 ClO4, [1 ClO4 ] = 0.83 mm. Conditions: [1 ClO4 ] = 0.8 mm, [nbu 4 NF 3H 2 O] = 1.6 mm. Inset: Kinetic profile of absorbance at 450 nm. 13

Supplementary Figure 14. HRMS (ESI-MS) spectrum of the orange intermediate species (2 ClO4 ) after its formation upon addition of 2 equiv. of tetrabutylammonium fluoride trihydrate to complex 1 ClO4 at 25ºC in CH 3 CN under N 2 confirmed by UV-Vis spectroscopy. Conditions: [1 ClO4 ] = 0.8 mm, [nbu 4 NF 3H 2 O] = 1.6 mm. Bottom: simulated spectrum. 14

Supplementary Figure 15. Variable temperature 1 H NMR monitoring of the fluorination of the model aryl halide substrate L 1 -Br using 1 equiv. of AgOTf and 1 equiv. of AgF. Conditions: [L 1 -Br] = 17.5 mm, CD 3 CN, 40ºC. (1 ClO4 = aryl-ag III species, P = L 1 -F). 15

Supplementary Figure 16. DFT computed reaction profile for the reductive elimination of L 5 -Ag(III)-F to Ag(I) and L 5 -F. Relative Gibbs energy values are given in kcal mol -1. Selected bond distances are given in Å. H atoms are omitted for clarity. 16

Supplementary Figure 17. DFT computed reaction profile for the oxidative addition of Ag(I) over L 1 -X, a) X = F, b) X = Cl, c) X = Br and d) X = I. Relative Gibbs energy values are given in kcal mol -1. Selected bond distances are given in Å. H atoms are omitted for clarity except for N-H moieties. a) 17

b) 18

c) 19

d) 20

Supplementary Figure 18. 1 H NMR monitoring of the C-O bond forming cross-coupling catalysis of the model aryl halide substrate L 1 -I. Conditions: [L 1 -I] = 20 mm, [p-no 2 phenol] = 0.4 M, [AgOTf] = 2 mm, [PPh 3 ] = 2 mm, CD 3 CN, 35ºC. (1 ClO4 = aryl-ag III species, P = 2d). 1 ClO4 is formed in a 4% yield and 2d in a 17% yield (the lower yield of 2d compared to the standard catalytic procedure (Table 2, main text) can be explained by the lower temperature employed and the absence of stirring in the NMR tube). 21

Supplementary Figure 19. Transmitted light monitoring of AgOTf solutions upon addition of nbu 4 NI. Red line corresponds to a sample containing AgOTf and 10 equiv. of nbuni in acetonitrile. Blue line corresponds to a sample containing AgOTf, 200 equiv. of p-nitrophenol and 1 equiv. of nbuni in acetonitrile. Green line corresponds to a sample containing AgOTf and 1 equiv. of nbu 4 NI in acetonitrile. Conditions: [AgOTf] = 0.63 mm, CH 3 CN, rt. 22

Supplementary Figure 20. HRMS (ESI-MS) spectrum in positive ion mode of the silver species formed upon addition of 200 equiv. of p-nitrophenol to a silver triflate solution at 25ºC in CH 3 CN. Conditions: [AgOTf] = 2.5 mm, [p-no 2 phenol] = 0.5 M. 23

Supplementary Figure 21. HRMS (ESI-MS) spectrum in positive ion mode of the silver species formed upon addition of 200 equiv. of p-cyanophenol to a silver triflate solution at 25ºC in CH 3 CN. Conditions: [AgOTf] = 2.5 mm, [p-cnphenol] = 5 mm. 24

Supplementary Figure 22. HRMS (ESI-MS) spectrum in negative ion mode of the C-O bond forming cross-coupling catalysis of the model aryl halide substrate L 1 -I at 50ºC in CH 3 CN under N 2 after 6 h. Conditions: [L 1 -I] = 5 mm, [p-no 2 phenol] = 0.1 M, [AgOTf] = 0.5 mm, [PPh 3 ] = 0.5 mm, CH 3 CN, 50ºC. 25

Supplementary Figure 23. HRMS (ESI-MS) spectrum in negative ion mode of the silver species formed upon addition of 1 equiv. of tetrabutylammonium iodide to a silver triflate and 20 equiv. of p-nitrophenol solution at 25ºC in CH 3 CN. Conditions: [AgOTf] = 2.5 mm, [p-no 2 phenol] = 50 mm, [nbu 4 NI] = 2.5 mm. 26

Supplementary Figure 24. HRMS (ESI-MS) spectrum in negative ion mode of the stoichiometric halide exchange reaction of the model aryl halide substrate L 1 -I at 50ºC in CH 3 CN under N 2 after 6 h. Conditions: [L 1 -I] = 15 mm, [nbu 4 Br] = 0.15 M, [AgOTf] = 15 mm, CH 3 CN, 50ºC. 27

28

Supplementary Figure 25. HRMS (ESI-MS) spectrum in positive ion mode of the C-O bond forming cross-coupling catalysis of the model aryl halide substrate L 1 -I at 50ºC in CH 3 CN under N 2 after 6 h. Conditions: [L 1 -I] = 5 mm, [p-no 2 phenol] = 0.1 M, [AgOTf] = 0.5 mm, [PPh 3 ] = 0.5 mm, CH 3 CN, 50ºC. 29

Supplementary Figure 26. Cyclic Voltammetry (CV) of complex [[Ag III (L 1 )](ClO 4 ) 2 ] = 1 mm, [nbu 4 NPF 6 ] = 0.1 M, CH 3 CN, 298 K, scan rate = 0.1 V/s, using non-aqueous Ag/AgNO 3 reference electrode and AcFc/AcFc + as the internal reference. Ag(0/Ag(I) AcFc/AcFc + Ag(II)/Ag(III) 30

Supplementary Figure 27. DFT free energy difference of the single electron transfer (SET) from the pno 2 -phenol to the aryl-ag(iii) complex. Relative Gibbs energy values are given in kcal mol -1. Selected bond distances are given in Å. 31

Supplementary Figure 28. DFT computed reaction profile for the reductive elimination of the aryl-ag(iii) complex with p-nitrophenol. Relative Gibbs energy values are given in kcal mol -1. Selected bond distances are given in Å. H atoms are omitted for clarity.. 32

Supplementary Figure 29. Eyring plot for the reaction of complex 1 ClO4 with p-cn-phenol obtained by UV-vis monitoring. Reaction conditions: [1 ClO4 ] = 0.8 mm, [p-cnphenol] = 8 mm, CH 3 CN, T range = 298-335.5 K. ΔH = 19.3 ± 0.6 kcal/mol ΔS = -17.2 ± 2 cal/mol K 33

Supplementary Figure 30. 1 H NMR spectrum of compound 2a in CD 3 CN, 400 MHz, at 298 K. 34

Supplementary Figure 31. 13 C NMR spectrum of compound 2a in CD 3 CN, 100 MHz, at 298 K. 35

Supplementary Figure 32. COSY spectrum of compound 2a in CD 3 CN, 400 MHz, at 298 K. 36

Supplementary Figure 33. NOESY spectrum of compound 2a in CD 3 CN, 400 MHz, at 298 K. 37

Supplementary Figure 34. 1 H 13 C HSQC spectrum of compound 2a in CD 3 CN, 400 MHz, at 298 K. 38

Supplementary Figure 35. HRMS (ESI-MS) spectrum of compound 2a in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 39

Supplementary Figure 36. 1 H NMR spectrum of compound 2b in CD 3 CN, 400 MHz, at 333 K. 40

Supplementary Figure 37. 13 C NMR spectrum of compound 2b in CD 3 CN, 100 MHz, at 333 K. 41

Supplementary Figure 38. COSY spectrum of compound 2b in CD 3 CN, 400 MHz, at 333 K. 42

Supplementary Figure 39. NOESY spectrum of compound 2b in CD 3 CN, 400 MHz, at 333 K. 43

Supplementary Figure 40. 1 H 13 C HSQC spectrum of compound 2b in CD 3 CN, 400 MHz, at 333 K. 44

Supplementary Figure 41. HRMS (ESI-MS) spectrum of compound 2b in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 45

Supplementary Figure 42. 1 H NMR spectrum of compound 2c in CD 3 CN, 400 MHz, at 333 K. 46

Supplementary Figure 43. 13 C NMR spectrum of compound 2c in CD 3 CN, 100 MHz, at 333 K. 47

Supplementary Figure 44. COSY spectrum of compound 2c in CD 3 CN, 400 MHz, at 333 K. 48

Supplementary Figure 45. NOESY spectrum of compound 2c in CD 3 CN, 400 MHz, at 333 K. 49

Supplementary Figure 46. 1 H 13 C HSQC spectrum of compound 2c in CD 3 CN, 400 MHz, at 333 K. 50

Supplementary Figure 47. HRMS (ESI-MS) spectrum of compound 2c in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 51

Supplementary Figure 48. 1 H NMR spectrum of compound 2d in CD 3 CN, 400 MHz, at 298 K. 52

Supplementary Figure 49. 13 C NMR spectrum of compound 2d in CD 3 CN, 100 MHz, at 298 K. 53

Supplementary Figure 50. COSY spectrum of compound 2d in CD 3 CN, 400 MHz, at 298 K. 54

Supplementary Figure 51. NOESY spectrum of compound 2d in CD 3 CN, 400 MHz, at 298 K. 55

Supplementary Figure 52. 1 H 13 C HSQC spectrum of compound 2d in CD 3 CN, 400 MHz, at 298 K. 56

Supplementary Figure 53. HRMS (ESI-MS) spectrum of compound 2d in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 57

Supplementary Figure 54. 1 H NMR spectrum of compound 2e in CD 3 CN, 400 MHz, at 298 K. 58

Supplementary Figure 55. 13 C NMR spectrum of compound 2e in CD 3 CN, 100 MHz, at 298 K. 59

Supplementary Figure 56. COSY spectrum of compound 2e in CD 3 CN, 400 MHz, at 298 K. 60

Supplementary Figure 57. NOESY spectrum of compound 2e in CD 3 CN, 400 MHz, at 298 K. 61

Supplementary Figure 58. 1 H 13 C HSQC spectrum of compound 2e in CD 3 CN, 400 MHz, at 298 K. 62

Supplementary Figure 59. HRMS (ESI-MS) spectrum of compound 2e in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 63

Supplementary Figure 60. 1 H NMR spectrum of compound 2f in CD 3 CN, 400 MHz, at 298 K. 64

Supplementary Figure 61. 13 C NMR spectrum of compound 2f in CD 3 CN, 100 MHz, at 298 K. 65

Supplementary Figure 62. COSY spectrum of compound 2f in CD 3 CN, 400 MHz, at 298 K. 66

Supplementary Figure 63. NOESY spectrum of compound 2f in CD 3 CN, 400 MHz, at 298 K. 67

Supplementary Figure 64. 1 H 13 C HSQC spectrum of compound 2f in CD 3 CN, 400 MHz, at 298 K. 68

Supplementary Figure 65. HRMS (ESI-MS) spectrum of compound 2f in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 69

Supplementary Figure 66. 1 H NMR spectrum of compound 2g in CD 3 CN, 400 MHz, at 298 K. 70

Supplementary Figure 67. 13 C NMR spectrum of compound 2g in CD 3 CN, 100 MHz, at 298 K. 71

Supplementary Figure 68. COSY spectrum of compound 2g in CD 3 CN, 400 MHz, at 298 K. 72

Supplementary Figure 69. NOESY spectrum of compound 2g in CD 3 CN, 400 MHz, at 298 K. 73

Supplementary Figure 70. 1 H 13 C HSQC spectrum of compound 2g in CD 3 CN, 400 MHz, at 298 K. 74

Supplementary Figure 71. HRMS (ESI-MS) spectrum of compound 2g in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 75

Supplementary Figure 72. 1 H NMR spectrum of compound L 1 -CN in CD 3 CN, 400 MHz, at 298 K. 76

Supplementary Figure 73. 13 C NMR spectrum of compound L 1 -CN in CD 3 CN, 100 MHz, at 298 K. 77

Supplementary Figure 74. COSY spectrum of compound L 1 -CN in CD 3 CN, 400 MHz, at 298 K. 78

Supplementary Figure 75. NOESY spectrum of compound L 1 -CN in CD 3 CN, 400 MHz, at 298 K. 79

Supplementary Figure 76. 1 H 13 C HSQC spectrum of compound L 1 -CN in CD 3 CN, 400 MHz, at 298 K. 80

Supplementary Figure 77. HRMS (ESI-MS) spectrum of compound L 1 -CN in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 81

Supplementary Figure 78. 1 H NMR spectrum of compound 2h in CD 3 CN, 400 MHz, at 298 K (see ref 2 ) 82

Supplementary Figure 79. 13 C NMR spectrum of compound 2h in CD 3 CN, 100 MHz, at 298 K. 83

Supplementary Figure 80. COSY spectrum of compound L 1 -CN in CD 3 CN, 400 MHz, at 298 K. 84

Supplementary Figure 81. NOESY spectrum of compound 2h in CD 3 CN, 400 MHz, at 298 K. 85

Supplementary Figure 82. 1 H 13 C HSQC spectrum of compound 2h in CD 3 CN, 400 MHz, at 298 K. 86

Supplementary Figure 83. HRMS (ESI-MS) spectrum of compound 2h in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 87

Supplementary Figure 84. 1 H NMR spectrum of compound 2i in CD 3 CN, 400 MHz, at 298 K. 88

Supplementary Figure 85. 13 C NMR spectrum of compound 2i in CD 3 CN, 100 MHz, at 298 K. 89

Supplementary Figure 86. COSY spectrum of compound 2i in CD 3 CN, 400 MHz, at 298 K. 90

Supplementary Figure 87. NOESY spectrum of compound 2i in CD 3 CN, 400 MHz, at 298 K. 91

Supplementary Figure 88. 1 H 13 C HSQC spectrum of compound 2i in CD 3 CN, 400 MHz, at 298 K. 92

Supplementary Figure 89. HRMS (ESI-MS) spectrum of compound 2i in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 93

Supplementary Figure 90. 1 H NMR spectrum of compound 2j in CD 3 CN, 400 MHz, at 298 K. 94

Supplementary Figure 91. 13 C NMR spectrum of compound 2j in CD 3 CN, 100 MHz, at 298 K. 95

Supplementary Figure 92. COSY spectrum of compound 2j in CD 3 CN, 400 MHz, at 298 K. 96

Supplementary Figure 93. NOESY spectrum of compound 2j in CD 3 CN, 400 MHz, at 298 K. 97

Supplementary Figure 94. 1 H 13 C HSQC spectrum of compound 2j in CD 3 CN, 400 MHz, at 298 K. 98

Supplementary Figure 95. HRMS (ESI-MS) spectrum of compound 2j in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 99

Supplementary Figure 96. 1 H NMR spectrum of compound L 1 -Cl in CD 3 CN, 400 MHz, at 298 K. 100

Supplementary Figure 97. HRMS (ESI-MS) spectrum of compound L 1 -Cl in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 101

Supplementary Figure 98. 1 H NMR spectrum of compound L 1 -Br in CD 3 CN, 400 MHz, at 298 K. 102

Supplementary Figure 99. HRMS (ESI-MS) spectrum of compound L 1 -Br in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 103

Supplementary Figure 100. 1 H NMR spectrum of compound L 1 -I in CD 3 CN, 400 MHz, at 298 K. 104

Supplementary Figure 101. HRMS (ESI-MS) spectrum of compound L 1 -I in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 105

Supplementary Figure 102. 1 H NMR spectrum of compound L 1 -F in CD 3 CN, 400 MHz, at 298 K. 106

Supplementary Figure 103. 19 F-NMR spectrum of compound L 1 -F in CD 3 CN, 282.4 MHz, at 298 K, using NaCF 3 SO 3 as internal standard (-79.0 ppm). 107

Supplementary Figure 104. 1 H NMR spectrum of compound L 5 -F in CD 3 CN, 400 MHz, at 298 K. 108

Supplementary Figure 105. 19 F-NMR spectrum of compound L 5 -F in CD 3 CN, 282.4 MHz, at 298 K, using NaCF 3 SO 3 as internal standard (-79.0 ppm). 109

Supplementary Figure 106. HRMS (ESI-MS) spectrum of compound L 5 -F in CH 3 CN (spectrum at the bottom corresponds to the simulated peak). 110

Supplementary Tables Supplementary Table 1. Optimization of the oxidative addition of silver(i) salts to the model aryl-halide L 1 -X ligands under N 2 atmosphere to afford 1 OTf in presence or absence of an additive in CH 3 CN at variable temperatures. a Entry Ligand Equiv. AgOTf Additive (equiv. NaOTf) Yield Entry Ligand Equiv AgOTf Additive (equiv. NaOTf) Yield b 1 c L 1-Cl 2 0 0% 13 L 1-Br 1.2 0 37% 2 L 1-Br 0.5 0 traces 14 1.6 0 55% 3 0.8 0 15% 15 2 0 79% 4 1 0 26% 16 2 2 83% 5 1 1 32% 17 3 0 71% 6 1 1.5 36% 18 d 1 1 (Tl(OTf)) 50% 7 1 2 49% 19 d 1 10 (Tl(OTf)) 58% 8 1 3 45% 20 d 0 10 (Tl(OTf)) 0% 9 1 4 42% 21 d L 1-I 1 2 51% 10 1 6 40% 22 d 2 0 97% 11 1 8 33% 23 d 1 1 (Tl(OTf)) 68% 12 1 10 32% 24 d 4 4 (Tl(OTf)) 78% a General conditions: [L 1-X] = 15 mm, [Ag I ] = 7.5-30 mm, [additive] = 0-150 mm, 1 ml CH 3CN, rt. b Calculated by 1 H NMR spectroscopy using 1,3,5-trimethoxybenzene as internal standard. c Reaction performed at 70ºC. d Reaction performed in CD 3CN. 111

Supplementary Table 2. Silver-catalyzed cross coupling with L 1 -X model substrates under N 2 atmosphere in CH 3 CN at 50ºC. a Entry Substrate Additive (mol%) AgOTf (mol%) 2d Yield b (mol%) 1 c L 1 -I - 10 mol% 9% 2 PPh 3 (1 mol%) 10 mol% 35% 3 PPh 3 (5 mol%) 10 mol% 44% 4 d PPh 3 (10 mol%) 10 mol% 46% 5 e,f PPh 3 (10 mol%) 10 mol% 38% 6 PPh 3 (20 mol 10 mol% %) 33% 7 PPh 3 (30 mol%) 10 mol% 34% 8 PPh 3 (50 mol%) 10 mol% 23% 9 P(C 6 F 5 ) 3 (10 10 mol% mol%) 31% 10 P(tBu) 3 (10 10 mol% mol%) 10% 11 P(nBu) 3 (10 10 mol% mol%) 26% 12 P(OMe) 3 (1 10 mol% mol%) 30% 13 P(NMe 2 ) 3 (10 10 mol% mol%) 38% 14 Ph 2 P-(CH 2 ) 3-10 mol% PPh 2 (10 mol%) 12% 15 DMEDA (10 10 mol% mol%) 40% 16 L 1 -Br PPh 3 (20 mol%) 10 mol% 13% 17 P(nBu) 3 (10 10 mol% mol%) 12% 18 + Tl(OTf) (2 <2% g PPh 3 (10 mol%) 0 mol% eq.) a General conditions: [L 1-X] = 5 mm, [p-no 2phenol] = 100 mm, 3 ml CH 3CN, 50ºC, 24 h. b Calculated by 1 H NMR spectroscopy using 1,3,5-trimethoxybenzene as internal standard. c [p-no 2phenol] = 10 mm; d [p-no 2phenol] = 300 mm. e 70ºC. f 18% intramolecular C-N coupling and 5% L 1-OH. 3 g TlOTf (2 equiv.) as additive, 25ºC. 112

Supplementary Table 3. Crystallographic data and structure refinement for complex [Ag III (L 1 )](ClO 4 ) 2 (1 ClO4 ); the Cambridge Crystallographic Data Centre (CCDC) code is 978368. Compound 1 ClO4 Empirical formula C 15 H 24 Ag Cl 2 N 3 O 8 Formula weight 553.14 Temperature, K 150(10) Wavelenght, Å 0.71073 Crystal system monoclinic Space group P21/n Unit cell dimensions a, Å 8.5454(4) α, deg 90.00 b, Å 12.5939(5) β, deg 94.839(4) c, Å 18.7061(8) γ, deg 90.00 Volume, Å 3 2005.97(14) Density (calculated), g cm 3 1.832 Cell formula units_z 4 Absorption coefficient, mm -1 1.321 Crystal size, mm 0.31 x 0.12 x 0.08 Reflections collected 27341 Independent reflections 5122 [R(int) = 0.0333] Final R indices [I<2σ(I)] α R1 = 0.0312, wr2 = 0.0700 R indices (all data) R1 = 0.0414, wr2 = 0.0775 2 2 2 4 1/ 2 [ F0 F ]/ F0 0 R c wr [ ( w( F0 Fc ) ) / ( wf )] 113

Supplementary Table 4. Optimized xyz cartesian coordinates (Å) for all compounds and transition states involved in the oxidative addition/reductive elimination steps. The absolute free energy values (G) for each silver intermediate are in atomic units. L 1 -Ag III -F -ACN (G = -1129.808771) 7 0.101619000-2.018861000-0.341410000 6 1.498339000-2.292726000-0.838668000 1 1.872824000-3.207852000-0.373016000 1 1.428016000-2.463003000-1.916187000 7-2.400893000 0.011229000 0.092837000 6-0.959677000-2.718024000-1.104477000 1-0.733310000-3.789800000-1.095242000 1-0.911387000-2.353646000-2.131558000 7 0.065788000 2.140317000 0.260249000 6-2.347526000-2.485401000-0.505332000 1-2.337017000-2.748932000 0.555971000 1-3.020196000-3.196314000-0.993253000 6-2.964940000-1.099344000-0.732631000 1-2.821350000-0.811818000-1.774997000 1-4.039860000-1.149058000-0.519697000 6-2.698635000-0.202939000 1.527983000 1-3.784883000-0.256821000 1.673559000 1-2.289896000 0.619547000 2.112076000 1-2.232022000-1.127466000 1.863320000 6-2.982444000 1.302289000-0.384169000 1-4.059420000 1.271240000-0.178974000 1-2.826724000 1.327910000-1.463880000 6-2.394420000 2.578068000 0.234007000 1-2.385341000 2.527500000 1.326634000 1-3.084761000 3.383965000-0.030249000 6-1.014460000 3.007535000-0.269227000 1-0.962265000 2.958071000-1.358085000 1-0.813184000 4.035932000 0.049493000 6 1.454604000 2.565687000-0.145398000 1 1.371289000 3.020824000-1.135645000 1 1.817535000 3.325995000 0.550279000 6 2.348123000 1.357009000-0.226801000 6 1.730315000 0.121047000-0.370571000 6 2.370466000-1.094012000-0.577922000 6 3.769486000-1.062100000-0.604837000 1 4.331190000-1.977372000-0.759052000 6 4.438579000 0.155436000-0.435743000 1 5.522705000 0.167401000-0.449650000 6 3.747199000 1.359340000-0.257292000 1 4.292080000 2.290882000-0.146149000 1 0.016888000 2.164322000 1.278554000 1 0.052422000-2.324562000 0.633013000 7 0.501659000-2.256065000 2.750917000 6 0.600176000-1.124416000 2.952262000 6 0.715917000 0.302674000 3.184397000 1 1.027341000 0.486699000 4.216332000 1 1.456861000 0.721027000 2.498630000 1-0.255020000 0.772935000 3.010305000 47-0.249389000 0.081180000-0.215287000 9-0.739451000 0.373318000-2.592852000 TS-L 1 -Ag-F -ACN (G = -1129.783946) 7-0.101088000 2.202123000 0.155468000 6-1.472354000 2.549183000-0.376117000 1-1.905516000 3.376762000 0.191756000 1-1.327195000 2.868490000-1.410327000 7 2.515353000 0.085030000 0.099961000 6 0.995387000 3.078318000-0.316353000 1 0.788365000 4.112243000-0.016477000 1 1.002499000 3.029688000-1.408148000 7-0.004512000-2.054921000-0.479637000 6 2.356429000 2.650160000 0.250423000 1 2.280668000 2.552523000 1.337668000 1 3.043393000 3.481254000 0.066173000 6 3.016514000 1.408217000-0.376901000 1 2.860067000 1.439015000-1.458336000 1 4.097893000 1.447224000-0.187635000 6 2.897559000-0.133530000 1.508937000 1 3.992736000-0.131452000 1.603835000 1 2.500808000-1.085162000 1.857549000 1 2.477995000 0.656116000 2.130842000 6 3.067047000-0.999898000-0.765104000 1 4.151433000-1.047153000-0.595427000 1 2.898464000-0.699014000-1.802436000 6 2.470025000-2.403564000-0.554965000 1 2.418382000-2.654558000 0.508311000 1 3.184237000-3.102554000-0.999954000 6 1.112720000-2.693795000-1.211516000 1 1.091518000-2.312472000-2.235346000 1 0.952460000-3.777944000-1.241861000 6-1.376059000-2.295848000-1.064527000 1-1.248879000-2.309076000-2.149149000 1-1.765138000-3.265528000-0.743188000 6-2.271545000-1.153814000-0.666242000 6-1.707089000 0.120949000-0.719732000 6-2.324936000 1.310250000-0.330607000 6-3.634822000 1.194108000 0.139401000 1-4.154190000 2.081568000 0.486872000 6-4.261545000-0.058156000 0.195939000 1-5.274254000-0.131557000 0.574696000 6-3.580991000-1.222725000-0.185790000 1-4.061521000-2.191441000-0.091897000 1-0.004344000-2.413974000 0.475928000 1-0.138457000 2.263139000 1.173014000 7 0.147101000-2.106768000 2.830353000 6-0.450831000-1.122236000 2.896697000 6-1.201533000 0.118844000 2.946915000 1-1.726640000 0.257448000 1.998495000 1-1.925183000 0.084089000 3.765826000 1-0.516831000 0.956940000 3.102080000 9-0.900731000 0.369672000-2.402523000 47 0.313021000 0.090028000-0.207998000 L 1 -Ag I -F -ACN (G = -1129.836831) 7 0.204830000-2.164264000-0.759592000 6 1.242046000-2.015500000-1.806512000 1 1.939979000-2.861081000-1.829157000 1 0.733340000-1.966220000-2.771452000 7-2.655107000-0.279462000 0.309372000 6-0.923936000-3.038254000-1.116248000 1-0.663667000-4.100089000-1.000585000 1-1.155923000-2.871678000-2.172511000 7-0.303844000 2.390355000 0.009155000 6-2.161235000-2.709185000-0.274498000 1-1.869945000-2.683851000 0.780651000 1-2.881971000-3.524914000-0.384793000 6-2.829403000-1.377463000-0.677077000 1-2.393090000-1.028603000-1.615906000 1-3.906868000-1.524494000-0.844446000 6-3.452918000-0.567036000 1.515980000 1-4.519299000-0.653806000 1.252897000 1-3.330452000 0.234181000 2.244926000 1-3.119701000-1.501156000 1.968364000 6-3.109832000 0.998803000-0.297179000 1-4.199620000 0.946807000-0.439470000 1-2.650009000 1.060285000-1.286394000 6-2.733170000 2.257529000 0.511978000 1-2.435063000 1.983224000 1.529152000 1-3.611535000 2.903482000 0.603050000 6-1.604923000 3.070746000-0.129531000 1-1.811236000 3.183753000-1.198097000 1-1.574894000 4.078476000 0.307703000 6 0.714161000 2.792386000-0.994444000 114

1 0.198854000 2.946199000-1.944423000 1 1.217025000 3.727142000-0.721260000 6 1.714981000 1.674084000-1.117051000 6 1.298182000 0.469774000-1.671213000 6 1.981759000-0.732301000-1.531637000 6 3.241244000-0.676640000-0.930595000 1 3.797872000-1.597957000-0.795707000 6 3.755004000 0.534485000-0.462950000 1 4.731003000 0.560479000 0.007176000 6 2.979636000 1.693677000-0.523040000 1 3.334777000 2.617443000-0.078710000 1 0.069522000 2.607784000 0.928984000 1 0.651049000-2.537259000 0.073569000 7 1.353450000-0.384041000 2.103039000 6 2.456940000-0.588037000 2.360873000 6 3.845550000-0.851373000 2.679643000 1 3.908184000-1.424089000 3.609192000 1 4.298175000-1.422544000 1.865158000 1 4.379869000 0.094764000 2.798439000 9 0.089183000 0.447063000-2.311830000 47-0.396146000-0.081322000 0.746113000 1 1.341961000 3.139614000-0.552986000 1 1.832815000 3.175478000 1.147512000 6 2.358360000 1.363357000 0.050630000 6 1.747224000 0.157323000-0.265155000 6 2.385772000-0.999342000-0.692359000 6 3.782611000-0.945728000-0.760634000 1 4.345032000-1.816104000-1.081712000 6 4.448482000 0.237039000-0.419032000 1 5.531257000 0.264805000-0.467372000 6 3.755417000 1.388392000-0.027657000 1 4.297253000 2.297810000 0.209833000 1 0.063819000 1.898792000 1.730586000 1 0.118338000-2.439101000 0.361148000 7 0.545001000-2.723311000 2.450449000 6 0.684258000-1.649078000 2.847470000 6 0.849716000-0.289300000 3.324692000 1 1.237247000-0.298737000 4.347043000 1 1.549695000 0.238359000 2.671838000 1-0.118511000 0.218064000 3.307258000 17-0.712137000 0.949835000-2.844964000 47-0.226597000 0.064274000-0.047434000 1-1.268795000-2.082875000-2.286487000 1-1.778333000-3.196586000-0.999083000 6-2.256415000-1.112233000-0.650112000 6-1.750574000 0.195152000-0.675676000 6-2.325104000 1.297879000-0.027579000 6-3.533589000 1.065224000 0.630498000 1-3.999550000 1.879789000 1.175659000 6-4.113904000-0.209382000 0.633135000 1-5.047150000-0.371591000 1.159491000 6-3.463861000-1.291687000 0.026708000 1-3.878150000-2.291826000 0.104010000 1 0.018943000-2.514478000 0.286985000 1-0.145853000 2.139464000 1.547268000 7 0.320189000-2.538243000 2.677086000 6-0.276842000-1.565099000 2.843459000 6-1.028648000-0.336632000 3.024143000 1-1.607628000-0.132112000 2.120693000 1-1.705392000-0.437446000 3.876947000 1-0.339703000 0.493028000 3.202640000 47 0.325206000 0.102027000-0.108102000 17-0.896300000 0.723641000-2.608775000 L 1 -Ag III -Cl -ACN (G = -1490.185748) TS-L 1 -Ag-Cl-ACN (G = -1490.159790 ) L 1 -Ag I -Cl-ACN (G = -1490.188651.) 7 0.130007000-1.974492000-0.550023000 6 1.510975000-2.142506000-1.131579000 1 1.902402000-3.122434000-0.847882000 1 1.404562000-2.118372000-2.219110000 7-2.369202000-0.070348000 0.288021000 6-0.953479000-2.550974000-1.382495000 1-0.717296000-3.605684000-1.559819000 1-0.946621000-2.017326000-2.334838000 7 0.083702000 2.030103000 0.719062000 6-2.320302000-2.439142000-0.704229000 1-2.270444000-2.871569000 0.299001000 1-3.004512000-3.070158000-1.278350000 6-2.956755000-1.043592000-0.683612000 1-2.857402000-0.593210000-1.672861000 1-4.021958000-1.140117000-0.441545000 6-2.613940000-0.515718000 1.681281000 1-3.694344000-0.585923000 1.857827000 1-2.171904000 0.197908000 2.373875000 1-2.146728000-1.485152000 1.843875000 6-2.985688000 1.271276000 0.050950000 1-4.049654000 1.187623000 0.302911000 1-2.890012000 1.472658000-1.017254000 6-2.377944000 2.440817000 0.836894000 1-2.327111000 2.220876000 1.907215000 1-3.080780000 3.271217000 0.726060000 6-1.019716000 2.952066000 0.352768000 1-1.003249000 3.050945000-0.734180000 1-0.810907000 3.926407000 0.806929000 6 1.457822000 2.532040000 0.348107000 7-0.120345000 2.188039000 0.529798000 6-1.500271000 2.556396000 0.044253000 1-1.957128000 3.307021000 0.694235000 1-1.373091000 2.981505000-0.953547000 7 2.539769000 0.080865000 0.157285000 6 0.967069000 3.108338000 0.130409000 1 0.784647000 4.107318000 0.544768000 1 0.943682000 3.179989000-0.960165000 7 0.002412000-2.043675000-0.616856000 6 2.344706000 2.613910000 0.603614000 1 2.298562000 2.383948000 1.672318000 1 3.026229000 3.464420000 0.506665000 6 2.999853000 1.459552000-0.183705000 1 2.805371000 1.607148000-1.249219000 1 4.087265000 1.502409000-0.028647000 6 2.981811000-0.292798000 1.512666000 1 4.080675000-0.287545000 1.564620000 1 2.608550000-1.283899000 1.764842000 1 2.582812000 0.413044000 2.240186000 6 3.058190000-0.892166000-0.848974000 1 4.150066000-0.948196000-0.735008000 1 2.842104000-0.475285000-1.836030000 6 2.481079000-2.321133000-0.778502000 1 2.453750000-2.683872000 0.253001000 1 3.197982000-2.957538000-1.306037000 6 1.114043000-2.570438000-1.437696000 1 1.063983000-2.073861000-2.410260000 1 0.985715000-3.648378000-1.595463000 6-1.376095000-2.201496000-1.205906000 7-0.194229000-2.112398000 0.858398000 6-1.236677000-1.895865000 1.892365000 1-1.951526000-2.725010000 1.934111000 1-0.743583000-1.824955000 2.862969000 7 2.623508000-0.345119000-0.496655000 6 0.968395000-2.898804000 1.301658000 1 0.724009000-3.968935000 1.368094000 1 1.235003000-2.561041000 2.307501000 7 0.260113000 2.347370000-0.348612000 6 2.169727000-2.700437000 0.370221000 1 1.834153000-2.809111000-0.665938000 1 2.880306000-3.510902000 0.557616000 6 2.890539000-1.349741000 0.565432000 1 2.565723000-0.909706000 1.510562000 1 3.978368000-1.505938000 0.625813000 6 3.296237000-0.755192000-1.743367000 1 4.382806000-0.836774000-1.577826000 1 3.109794000-0.021664000-2.528021000 1 2.913098000-1.719876000-2.076946000 6 3.145631000 0.977170000-0.064231000 1 4.245042000 0.926991000-0.052257000 1 2.811543000 1.132692000 0.963616000 6 2.676280000 2.166816000-0.926814000 1 2.322598000 1.817404000-1.902325000 1 3.531892000 2.821266000-1.118379000 6 1.575216000 3.010202000-0.273798000 1 1.814307000 3.155175000 0.783650000 1 1.542683000 4.003715000-0.743022000 6-0.750981000 2.866497000 0.610417000 115

1-0.229510000 3.194518000 1.510544000 1-1.294244000 3.724515000 0.200486000 6-1.710560000 1.742949000 0.911326000 6-1.279937000 0.611957000 1.614190000 6-1.952438000-0.613573000 1.546316000 6-3.201790000-0.631297000 0.921009000 1-3.735637000-1.573526000 0.857605000 6-3.730372000 0.520188000 0.340277000 1-4.699305000 0.488430000-0.143913000 6-2.964592000 1.683586000 0.296680000 1-3.313252000 2.552406000-0.251438000 1-0.108797000 2.485395000-1.285458000 1-0.627915000-2.595563000 0.076751000 7-1.392746000-0.618896000-2.163364000 6-2.498205000-0.833437000-2.404796000 6-3.890260000-1.105052000-2.701777000 1-3.963881000-1.689430000-3.623227000 1-4.331939000-1.667836000-1.875375000 1-4.428231000-0.161594000-2.825420000 17 0.230621000 0.708230000 2.545488000 47 0.329833000-0.168789000-0.779618000 1-1.184184000-2.537509000 1.784616000 1-1.848987000-1.503363000 3.061751000 6-2.355039000-0.937279000 1.012739000 6-1.768861000-0.253223000-0.043533000 6-2.418303000 0.225539000-1.172673000 6-3.804832000 0.037296000-1.214920000 1-4.375299000 0.391580000-2.067071000 6-4.449319000-0.614803000-0.157350000 1-5.524664000-0.747412000-0.196395000 6-3.741883000-1.110803000 0.944327000 1-4.264282000-1.632266000 1.739447000 1-0.230179000 0.054166000 2.677050000 1-0.310624000 2.188068000-1.391660000 7-0.891235000 3.807319000-0.071731000 6-1.025979000 3.294272000 0.952670000 6-1.183724000 2.629453000 2.231993000 1-1.649251000 3.310100000 2.950032000 1-1.813823000 1.745600000 2.103072000 1-0.200469000 2.328280000 2.601908000 47 0.174843000 0.136506000 0.109461000 35 0.820403000-2.449884000-1.209428000 1 1.364479000 1.013842000-2.722489000 1 1.663713000 2.649940000-2.098842000 6 2.176424000 1.046622000-0.734296000 6 1.759235000-0.178346000-0.189292000 6 2.270280000-0.749516000 0.986810000 6 3.330781000-0.074197000 1.592753000 1 3.737639000-0.462505000 2.520934000 6 3.832471000 1.112268000 1.044566000 1 4.650819000 1.625482000 1.535743000 6 3.236587000 1.682825000-0.086748000 1 3.571126000 2.648219000-0.452951000 1-0.245921000 2.490369000-0.796325000 1-0.079954000-1.023938000 2.545994000 7-0.642364000 3.795678000 1.122941000 6-0.263417000 2.966390000 1.829862000 6 0.211969000 1.906117000 2.698972000 1 1.037256000 1.380016000 2.210993000 1 0.555100000 2.326971000 3.648033000 1-0.603888000 1.201646000 2.883584000 47-0.384264000-0.045235000 0.058869000 35 1.177336000-1.740095000-1.778754000 L 1 -Ag III -Br -ACN (G = -3604.113179.) TS-L 1 -Ag-Br-ACN (G =-3604.091470 ) L 1 -Ag I -Br -ACN (G = -3604.114432) 7-0.227603000 1.216528000-1.698677000 6-1.556757000 0.793365000-2.267977000 1-2.015051000 1.638416000-2.787629000 1-1.354420000 0.009155000-3.002390000 7 2.270331000 0.669113000 0.325729000 6 0.899148000 1.112480000-2.655441000 1 0.648173000 1.701573000-3.544344000 1 0.981271000 0.059904000-2.935134000 7-0.131898000-0.739770000 2.045111000 6 2.214382000 1.620699000-2.060419000 1 2.075264000 2.632414000-1.669004000 1 2.918208000 1.706589000-2.893158000 6 2.897369000 0.709619000-1.030910000 1 2.894559000-0.316372000-1.403700000 1 3.935619000 1.037873000-0.899381000 6 2.373172000 1.994263000 0.983307000 1 3.428722000 2.283921000 1.057333000 1 1.934376000 1.943016000 1.977860000 1 1.824223000 2.733850000 0.403952000 6 2.960600000-0.375671000 1.142625000 1 3.990555000-0.034597000 1.302783000 1 2.980298000-1.282720000 0.535553000 6 2.325741000-0.698239000 2.503087000 1 2.161758000 0.208350000 3.092822000 1 3.070321000-1.287468000 3.045731000 6 1.043269000-1.533966000 2.476567000 1 1.134967000-2.365428000 1.775020000 1 0.840730000-1.927358000 3.478543000 6-1.428436000-1.506426000 2.053355000 7 0.060580000-1.535497000 1.676566000 6 1.516552000-1.913350000 1.581088000 1 1.914073000-2.195394000 2.559411000 1 1.572170000-2.779306000 0.917464000 7-2.609710000-0.122724000 0.103049000 6-0.907716000-2.652195000 1.627805000 1-0.738495000-3.339096000 2.466206000 1-0.726746000-3.198837000 0.698002000 7-0.102471000 1.656485000-1.364409000 6-2.362094000-2.151459000 1.680033000 1-2.476503000-1.469449000 2.527858000 1-2.979200000-3.025351000 1.909244000 6-2.965079000-1.542675000 0.396130000 1-2.638737000-2.137399000-0.461460000 1-4.060395000-1.612422000 0.458921000 6-3.188711000 0.779383000 1.115181000 1-4.285075000 0.691129000 1.116662000 1-2.907284000 1.808647000 0.897609000 1-2.802106000 0.524394000 2.101352000 6-3.077119000 0.253193000-1.264490000 1-4.175903000 0.283152000-1.251281000 1-2.771251000-0.550032000-1.939987000 6-2.556515000 1.595572000-1.820380000 1-2.646362000 2.388398000-1.071885000 1-3.240384000 1.864195000-2.631159000 6-1.138186000 1.628396000-2.419417000 1-0.960844000 0.738916000-3.030294000 1-1.046129000 2.510623000-3.064813000 6 1.329570000 1.644236000-1.830906000 7-0.213399000-1.082250000 1.991754000 6-1.210147000-0.170828000 2.608697000 1-1.934144000-0.714714000 3.225006000 1-0.680017000 0.530766000 3.254641000 7 2.543043000-0.919419000-0.303427000 6 0.970690000-1.361742000 2.819065000 1 0.725182000-2.038098000 3.650728000 1 1.301982000-0.414978000 3.255861000 7 0.227316000 1.223305000-2.007245000 6 2.113183000-1.960446000 1.989642000 1 1.711876000-2.756602000 1.354570000 1 2.815495000-2.435024000 2.681387000 6 2.884256000-0.927259000 1.142605000 1 2.668974000 0.071267000 1.528161000 1 3.967963000-1.094310000 1.238658000 6 3.084368000-2.132316000-0.945242000 1 4.179697000-2.167471000-0.827995000 1 2.838959000-2.132447000-2.007435000 1 2.648234000-3.022386000-0.491235000 6 3.138255000 0.284504000-0.939600000 1 4.231646000 0.159621000-0.957573000 1 2.915940000 1.134430000-0.290944000 6 2.618550000 0.593871000-2.358405000 1 2.215349000-0.309986000-2.826414000 1 3.465945000 0.912769000-2.972702000 6 1.561272000 1.703382000-2.415273000 1 1.848353000 2.507149000-1.731527000 1 1.530364000 2.129881000-3.427754000 6-0.743925000 2.301154000-1.675742000 116

1-0.188124000 3.162959000-1.303754000 1-1.306637000 2.619702000-2.559059000 6-1.689229000 1.759740000-0.631435000 6-1.238768000 1.439145000 0.654614000 6-1.922656000 0.542725000 1.485067000 6-3.199901000 0.138556000 1.085779000 1-3.741618000-0.558635000 1.716009000 6-3.745963000 0.570309000-0.121041000 1-4.736949000 0.246313000-0.416395000 6-2.971664000 1.333539000-0.991453000 1-3.336315000 1.576039000-1.983959000 1-0.161481000 0.689994000-2.780083000 1-0.679034000-1.963202000 1.793156000 7-1.543023000-2.089068000-1.169607000 6-2.664482000-2.350781000-1.187880000 6-4.077155000-2.673029000-1.204708000 1-4.210957000-3.737881000-1.414844000 1-4.511981000-2.434053000-0.230771000 1-4.576549000-2.083655000-1.978104000 47 0.237188000-0.837586000-0.545202000 35 0.437496000 2.200514000 1.275954000 L 1 -Ag III -I -ACN (G = -1041.391896.) 7-0.751718000 0.417910000-1.973767000 6-1.254732000-0.944041000-2.382426000 1-2.001758000-0.828728000-3.171409000 1-0.401368000-1.489951000-2.794035000 7 0.839590000 2.314657000 0.136900000 6 0.333107000 0.942628000-2.838196000 1-0.035259000 0.954910000-3.869508000 1 1.168431000 0.242884000-2.769014000 7-0.345998000 0.089425000 2.194148000 6 0.768279000 2.351315000-2.431824000 1-0.100544000 3.014730000-2.405023000 1 1.413391000 2.719354000-3.234343000 6 1.596691000 2.460618000-1.144972000 1 2.361956000 1.681561000-1.146349000 1 2.089759000 3.439745000-1.120187000 6-0.125518000 3.429351000 0.300712000 1 0.413778000 4.384103000 0.278823000 1-0.647169000 3.322421000 1.249918000 1-0.860808000 3.397031000-0.500955000 6 1.817328000 2.300126000 1.268606000 1 2.284157000 3.291707000 1.306359000 1 2.582668000 1.564021000 1.015239000 6 1.242074000 1.964992000 2.650485000 1 0.379223000 2.593566000 2.889420000 1 2.022641000 2.226331000 3.370269000 6 0.894378000 0.496918000 2.898786000 1 1.693101000-0.158284000 2.545522000 1 0.742961000 0.329972000 3.970393000 6-0.768277000-1.332472000 2.470841000 1 0.147491000-1.913669000 2.608115000 1-1.339040000-1.363303000 3.401811000 6-1.518589000-1.874212000 1.285028000 6-1.298240000-1.251740000 0.063947000 6-1.766175000-1.676391000-1.172011000 6-2.581495000-2.813948000-1.165738000 1-2.983865000-3.200244000-2.096195000 6-2.864792000-3.456996000 0.044886000 1-3.502862000-4.333526000 0.038637000 6-2.336234000-3.009487000 1.261463000 1-2.551642000-3.544490000 2.180364000 1-1.100963000 0.703848000 2.499959000 1-1.541329000 1.067726000-2.016914000 7-3.347104000 2.054114000-1.383583000 6-3.388046000 1.869318000-0.245574000 6-3.404417000 1.622308000 1.183662000 1-4.374080000 1.906752000 1.600975000 1-3.223946000 0.559454000 1.365931000 1-2.616718000 2.212650000 1.659139000 47-0.250137000 0.438855000 0.095862000 53 2.545335000-1.585079000-0.310649000 TS-L 1 -Ag-I-ACN (G = -1041,362100) 7 0.010794000-0.190141000 2.308301000 6 1.510597000-0.211379000 2.435277000 1 1.828911000 0.150680000 3.416556000 1 1.820824000-1.253491000 2.331643000 7-2.643363000-0.572287000 0.116792000 6-0.691721000-1.389432000 2.813111000 1-0.524407000-1.507123000 3.891368000 1-0.254603000-2.252171000 2.302817000 7-0.338014000 0.860219000-2.013470000 6-2.206624000-1.329180000 2.544390000 1-2.590630000-0.356256000 2.866365000 1-2.667103000-2.070019000 3.205041000 6-2.694979000-1.675227000 1.119785000 1-2.079540000-2.490131000 0.729786000 1-3.733046000-2.033375000 1.181454000 6-3.632486000 0.468919000 0.440968000 1-4.648399000 0.046093000 0.415302000 1-3.561689000 1.285554000-0.275998000 1-3.436718000 0.872816000 1.433880000 6-2.881269000-1.108788000-1.254908000 1-3.930602000-1.432606000-1.317048000 1-2.248560000-1.993058000-1.367316000 6-2.593666000-0.143257000-2.425385000 1-2.996913000 0.852577000-2.219306000 1-3.162549000-0.530769000-3.276014000 6-1.135948000-0.009923000-2.903021000 1-0.650179000-0.989767000-2.912579000 1-1.132730000 0.383425000-3.927691000 6 1.122604000 0.977805000-2.352163000 1 1.420810000 0.025365000-2.796037000 1 1.296235000 1.771945000-3.083218000 6 1.893707000 1.226444000-1.078385000 6 1.684056000 0.354909000 0.005118000 6 2.096465000 0.623533000 1.322814000 6 2.858472000 1.776433000 1.519341000 1 3.169391000 2.031987000 2.527284000 6 3.170112000 2.622550000 0.449475000 1 3.753831000 3.518578000 0.625373000 6 2.655779000 2.368627000-0.826532000 1 2.812876000 3.079174000-1.631781000 1-0.749587000 1.791277000-2.005656000 1-0.345442000 0.630833000 2.793092000 7-1.946460000 3.528731000-0.807568000 6-1.333527000 3.425155000 0.164329000 6-0.553667000 3.272855000 1.379646000 1 0.352094000 2.702865000 1.158572000 1-0.279210000 4.256399000 1.770685000 1-1.142265000 2.734518000 2.127132000 47-0.507914000 0.115103000 0.123397000 53 1.629491000-2.028700000-0.587074000 L 1 -Ag I -I -ACN (G = -1041.379904) 7 0.138004000-0.210881000-2.287614000 6 0.927150000 1.037586000-2.477973000 1 1.617026000 0.949237000-3.323264000 1 0.234956000 1.852784000-2.691337000 7-2.233910000-1.638166000-0.002868000 6-1.137754000-0.248733000-3.025093000 1-0.961516000-0.359232000-4.104742000 1-1.636168000 0.712051000-2.870368000 7 0.036358000-0.109530000 2.323460000 6-2.055009000-1.379457000-2.540339000 1-1.468207000-2.297490000-2.433374000 1-2.786362000-1.569061000-3.331988000 6-2.828873000-1.071518000-1.241424000 1-2.875192000 0.011350000-1.110714000 1-3.862599000-1.441311000-1.326776000 6-2.447050000-3.096315000 0.023968000 1-3.525360000-3.325186000 0.005140000 1-2.008925000-3.522386000 0.926900000 1-1.969545000-3.560435000-0.839445000 6-2.880523000-1.017712000 1.182698000 1-3.919234000-1.379171000 1.237305000 1-2.913210000 0.058927000 1.004399000 6-2.166274000-1.272567000 2.526648000 1-1.575200000-2.193005000 2.483652000 1-2.932355000-1.430555000 3.291911000 6-1.271931000-0.120433000 3.003435000 1-1.764141000 0.830706000 2.783714000 1-1.144712000-0.182883000 4.093647000 6 0.807140000 1.154694000 2.487581000 1 0.099672000 1.973125000 2.624236000 1 1.454605000 1.115493000 3.369453000 117

6 1.641153000 1.344555000 1.242862000 6 1.045189000 1.586112000-0.002832000 6 1.701405000 1.285327000-1.204901000 6 3.059891000 0.957217000-1.141696000 1 3.577938000 0.721464000-2.065618000 6 3.724131000 0.877473000 0.079719000 1 4.776895000 0.623099000 0.111428000 6 3.001537000 1.017492000 1.261874000 1 3.474402000 0.830307000 2.220403000 1 0.598059000-0.863274000 2.709591000 1 0.709675000-0.987016000-2.609236000 7 2.024048000-2.309720000 0.078653000 6 3.174222000-2.359658000 0.037471000 6 4.621422000-2.420745000-0.016615000 1 4.943939000-3.463162000-0.089456000 1 4.975070000-1.867358000-0.890425000 1 5.039874000-1.973085000 0.888429000 47 0.042561000-1.154809000 0.041819000 53-0.969929000 2.400948000-0.075144000 L 5 -Ag III -F -ACN (G = -1208.389280) 7-0.647360000 1.974749000 0.834453000 6-2.154233000 2.071755000 0.738768000 1-2.537265000 2.606084000 1.613001000 1-2.383010000 2.661417000-0.151961000 7 2.065895000 0.807049000-0.654543000 6-0.004246000 3.213317000 0.310335000 1-0.305237000 4.037428000 0.968212000 1-0.418612000 3.387754000-0.683992000 7 0.068259000-1.828804000-0.974057000 6 1.522602000 3.160983000 0.224641000 1 1.964768000 2.931769000 1.195746000 1 1.834866000 4.182167000-0.013346000 6 2.107396000 2.282839000-0.886790000 1 1.554754000 2.464550000-1.809956000 1 3.157522000 2.559042000-1.042106000 6 2.937048000 0.434993000 0.482143000 1 3.969610000 0.734655000 0.262465000 1 2.897117000-0.639929000 0.641636000 1 2.597964000 0.931484000 1.388155000 6 2.521297000 0.128364000-1.906042000 1 3.574335000 0.396582000-2.056228000 1 1.924313000 0.550784000-2.714881000 6 2.386867000-1.397695000-1.938146000 1 2.864118000-1.865203000-1.075262000 1 2.960237000-1.723996000-2.810875000 6 0.971945000-1.943156000-2.154139000 1 0.493819000-1.393093000-2.965054000 1 1.025918000-3.005860000-2.419321000 6-1.337853000-2.261563000-1.326041000 1-1.501199000-2.005812000-2.375430000 1-1.417591000-3.347330000-1.221464000 6-2.326869000-1.499153000-0.488503000 6-1.926523000-0.247990000-0.043161000 6-2.739812000 0.698589000 0.562042000 6-4.059612000 0.312741000 0.822519000 1-4.743767000 1.005059000 1.301607000 6-4.493728000-0.963823000 0.446969000 1-5.515073000-1.257904000 0.661215000 6-3.651045000-1.862484000-0.217690000 1-4.023930000-2.831613000-0.531809000 7 3.042128000-2.944528000 2.954048000 6 2.244458000-2.115848000 3.044068000 6 1.241870000-1.068608000 3.133351000 1 0.864924000-0.835569000 2.135452000 1 0.413501000-1.403078000 3.764087000 1 1.687100000-0.170163000 3.566478000 9-0.457316000 1.056353000-2.581246000 47-0.021703000 0.253280000-0.337564000 6-0.277637000 1.736850000 2.253035000 1-0.548996000 2.622361000 2.839226000 1-0.824183000 0.867212000 2.615363000 1 0.788819000 1.551217000 2.333987000 6 0.551928000-2.660894000 0.155793000 1-0.165641000-2.599253000 0.973245000 1 0.643948000-3.698572000-0.184227000 1 1.517171000-2.298118000 0.494569000 TS-L 5 -Ag-F -ACN (G = -1208.375606) 7-0.034476000 2.189068000-0.214951000 6-1.340374000 2.438841000-0.945033000 1-1.790348000 3.373571000-0.596485000 1-1.093325000 2.533478000-2.003364000 7 2.558446000 0.000645000-0.006574000 6 1.101657000 2.910446000-0.847503000 1 0.927978000 3.988595000-0.733378000 1 1.082354000 2.665942000-1.911797000 7-0.035074000-2.185189000-0.231757000 6 2.480556000 2.560179000-0.269005000 1 2.487108000 2.673744000 0.816512000 1 3.162448000 3.324735000-0.653724000 6 3.088765000 1.215498000-0.692692000 1 2.914338000 1.077919000-1.762897000 1 4.174133000 1.248802000-0.525327000 6 2.950198000-0.004311000 1.415905000 1 4.046277000-0.005885000 1.502878000 1 2.542348000-0.886698000 1.906556000 1 2.544718000 0.876312000 1.911668000 6 3.089024000-1.209246000-0.701184000 1 4.174217000-1.244187000-0.532954000 1 2.915842000-1.063795000-1.770586000 6 2.479816000-2.556657000-0.287859000 1 2.485703000-2.678160000 0.796795000 1 3.161497000-3.318778000-0.677768000 6 1.101044000-2.901756000-0.869760000 1 1.082168000-2.648626000-1.932036000 1 0.926847000-3.980720000-0.764425000 6-1.340942000-2.429124000-0.963902000 1-1.093843000-2.515747000-2.022874000 1-1.791091000-3.366425000-0.622564000 6-2.237832000-1.239607000-0.759951000 6-1.633564000 0.004741000-0.919245000 6-2.237499000 1.247970000-0.750258000 6-3.578312000 1.223801000-0.361352000 1-4.095253000 2.159955000-0.176275000 6-4.242930000 0.002186000-0.183207000 1-5.279585000 0.001105000 0.132539000 6-3.578637000-1.218174000-0.370930000 1-4.095773000-2.155626000-0.193124000 9-0.676977000 0.010707000-2.578571000 47 0.347964000 0.002004000-0.290709000 6-0.198031000-2.601830000 1.180866000 1-1.107759000-2.153207000 1.574953000 1-0.283694000-3.694981000 1.229845000 1 0.653399000-2.269599000 1.771686000 6-0.196987000 2.594199000 1.201038000 1-0.283186000 3.686882000 1.258899000 1-1.106143000 2.141884000 1.592159000 1 0.655128000 2.257519000 1.788470000 7 0.401281000-0.034144000 3.834699000 6-0.651455000-0.023985000 3.364216000 6-1.971468000-0.011099000 2.757715000 1-2.526563000-0.902082000 3.061540000 1-2.516078000 0.881116000 3.076466000 1-1.864821000-0.002672000 1.672024000 L 5 -Ag I -F -ACN (G = -1208.430445) 7 0.050484000 2.505990000-0.434220000 6-0.871578000 2.480347000-1.585446000 1-1.520367000 3.368959000-1.606006000 1-0.279254000 2.471515000-2.501625000 7 2.642048000 0.000411000 0.258497000 6 1.321214000 3.205079000-0.676466000 1 1.242511000 4.265613000-0.388204000 1 1.542258000 3.175051000-1.746740000 7 0.051082000-2.506025000-0.434019000 6 2.474250000 2.537136000 0.080948000 1 2.163659000 2.367232000 1.116360000 1 3.323358000 3.226138000 0.113079000 6 2.906900000 1.208433000-0.571177000 1 2.358520000 1.067930000-1.504326000 1 3.979731000 1.226460000-0.810540000 6 3.543894000 0.000464000 1.430481000 1 4.591725000 0.000222000 1.093878000 1 3.360620000-0.885478000 2.038217000 1 3.360944000 0.886722000 2.037859000 6 2.906975000-1.207648000-0.571146000 1 3.979750000-1.225443000-0.810776000 1 2.358300000-1.067334000-1.504142000 118

6 2.474825000-2.536439000 0.081151000 1 2.164132000-2.366569000 1.116544000 1 3.324186000-3.225122000 0.113376000 6 1.322008000-3.204830000-0.676191000 1 1.543037000-3.174912000-1.746471000 1 1.243575000-4.265332000-0.387769000 6-0.870886000-2.480575000-1.585359000 1-0.278451000-2.471545000-2.501461000 1-1.519419000-3.369367000-1.606008000 6-1.710663000-1.229943000-1.511530000 6-1.116307000-0.000148000-1.770009000 6-1.711017000 1.229481000-1.511573000 6-3.029048000 1.208909000-1.049406000 1-3.519956000 2.151414000-0.832132000 6-3.693497000-0.000506000-0.840321000 1-4.712818000-0.000644000-0.472647000 6-3.028703000-1.209736000-1.049375000 1-3.519345000-2.152374000-0.832078000 7-1.395856000-0.000175000 1.974926000 6-2.513590000 0.000081000 2.244702000 6-3.919980000 0.000409000 2.587289000 1-4.031859000 0.001052000 3.675199000 1-4.394619000 0.892256000 2.170179000 1-4.394767000-0.891846000 2.171218000 9 0.162007000 0.000030000-2.260837000 47 0.467622000-0.000129000 0.866916000 6-0.617844000 3.031526000 0.756674000 1-0.891449000 4.092915000 0.624761000 1-1.522022000 2.456077000 0.960257000 1 0.045403000 2.942049000 1.620482000 6-0.617245000-3.031870000 0.756764000 1-1.521563000-2.456640000 0.960341000 1-0.890605000-4.093295000 0.624675000 1 0.045934000-2.942357000 1.620618 L 1 -Ag III -p-no 2 phenol -ACN (G = -1541.396601) 7-1.384947000 1.258655000 1.638654000 6-0.204491000 2.194414000 1.760434000 1-0.565489000 3.175037000 2.079679000 1 0.443399000 1.799452000 2.546514000 7-2.857051000-1.339022000 0.409152000 6-1.710093000 0.533320000 2.891155000 1-1.843791000 1.276607000 3.684317000 1-0.849734000-0.091302000 3.137768000 7-0.716250000-0.722635000-1.985353000 6-2.981902000-0.304066000 2.759565000 1-3.811000000 0.336945000 2.447244000 1-3.225788000-0.654929000 3.766176000 6-2.891998000-1.564276000 1.887603000 1-1.982806000-2.114085000 2.138206000 1-3.760785000-2.199585000 2.098213000 6-4.109026000-0.692136000-0.052931000 1-4.968357000-1.307906000 0.239736000 1-4.084916000-0.585370000-1.135933000 1-4.194535000 0.299938000 0.386378000 6-2.667579000-2.656351000-0.274411000 1-3.588564000-3.232450000-0.124390000 1-1.846558000-3.160049000 0.234683000 6-2.355418000-2.594233000-1.776074000 1-3.075233000-1.967220000-2.310905000 1-2.494605000-3.611513000-2.152137000 6-0.930910000-2.181174000-2.153774000 1-0.199064000-2.684562000-1.522177000 1-0.743431000-2.428318000-3.204246000 6 0.652007000-0.245958000-2.402401000 1 1.357892000-1.035028000-2.132002000 1 0.672895000-0.114826000-3.486838000 6 0.995257000 1.002023000-1.637795000 6 0.304899000 1.224129000-0.453811000 6 0.554562000 2.233641000 0.464256000 6 1.582011000 3.125629000 0.137909000 1 1.834145000 3.934871000 0.814980000 6 2.291650000 2.959325000-1.056443000 1 3.084523000 3.657603000-1.299816000 6 2.016681000 1.908526000-1.939305000 1 2.598039000 1.790651000-2.847456000 1-1.402404000-0.235193000-2.562249000 1-2.197043000 1.822174000 1.374366000 7-3.347652000 3.065886000 0.001995000 6-3.112923000 2.657980000-1.051247000 6-2.800800000 2.120566000-2.362176000 1-3.230149000 2.759502000-3.138686000 1-1.714955000 2.078217000-2.483354000 1-3.220202000 1.114488000-2.448675000 47-1.179000000-0.032724000-0.031804000 8 0.269970000-2.191674000 0.820423000 6 1.474757000-1.791761000 0.754153000 6 2.434639000-2.389849000-0.142275000 6 1.953846000-0.687925000 1.549269000 6 3.709983000-1.895614000-0.271264000 1 2.111347000-3.232736000-0.743673000 6 3.226574000-0.194756000 1.417991000 1 1.257849000-0.230850000 2.242278000 6 4.121754000-0.784904000 0.497706000 1 4.407303000-2.343748000-0.967440000 1 3.554054000 0.653372000 2.005211000 7 5.424987000-0.252358000 0.335527000 8 6.204828000-0.781828000-0.483007000 8 5.767262000 0.740487000 1.010382000 TS-L 1 -Ag-p-NO 2 phenol -ACN (G = -1541.370187) 7-2.031449000 0.876381000 1.901500000 6-1.008939000 1.924595000 2.272353000 1-1.477997000 2.745873000 2.820376000 1-0.286096000 1.427036000 2.922776000 7-2.681311000-1.986649000 0.201867000 6-2.386096000-0.063493000 2.989377000 1-2.815820000 0.495780000 3.828698000 1-1.458972000-0.533645000 3.326694000 7-0.427030000-0.544864000-1.858861000 6-3.389257000-1.129739000 2.524790000 1-4.237903000-0.639464000 2.038218000 1-3.785381000-1.597746000 3.430709000 6-2.835891000-2.277346000 1.658185000 1-1.847754000-2.553410000 2.035673000 1-3.494680000-3.150507000 1.759811000 6-4.002711000-1.841582000-0.438419000 1-4.572214000-2.776515000-0.334478000 1-3.878348000-1.602876000-1.493197000 1-4.554238000-1.027944000 0.031510000 6-1.906893000-3.085806000-0.447113000 1-2.528049000-3.991814000-0.428892000 1-1.025889000-3.266925000 0.174157000 6-1.444479000-2.825883000-1.892641000 1-2.250724000-2.394864000-2.493394000 1-1.233025000-3.808869000-2.323392000 6-0.172121000-1.986647000-2.076818000 1 0.597721000-2.291555000-1.363942000 1 0.215258000-2.139060000-3.091262000 6 0.780403000 0.347400000-2.006676000 1 1.639581000-0.230845000-1.657773000 1 0.943532000 0.603380000-3.056873000 6 0.588392000 1.569862000-1.150376000 6 0.030143000 1.377162000 0.114394000 6-0.322492000 2.383679000 1.015742000 6-0.055716000 3.691256000 0.614618000 1-0.328168000 4.514946000 1.266648000 6 0.536158000 3.943426000-0.632519000 1 0.728245000 4.966346000-0.934511000 6 0.833952000 2.897072000-1.513065000 1 1.235343000 3.109926000-2.498873000 1-1.127987000-0.240273000-2.534746000 1-2.881001000 1.359974000 1.611369000 7-3.292536000 0.655538000-2.986630000 6-3.305433000 1.471805000-2.171364000 6-3.298325000 2.485242000-1.131789000 1-3.683527000 3.428202000-1.529043000 1-3.926386000 2.157730000-0.298775000 1-2.275097000 2.626582000-0.773943000 47-1.401154000-0.168132000 0.074150000 8 0.880159000-0.051234000 1.123024000 6 2.151104000-0.191537000 0.839422000 6 3.024962000 0.923695000 0.734205000 6 2.686180000-1.492421000 0.641867000 6 4.364351000 0.743606000 0.452759000 1 2.625595000 1.918999000 0.880624000 6 4.027971000-1.674018000 0.376704000 1 2.015617000-2.341483000 0.701517000 6 4.868666000-0.553923000 0.276197000 1 5.030402000 1.592663000 0.377512000 119