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Cordelia Baker
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1 Supplementary Figures Supplementary Figure 1. DFT optimized structure of the [Ag III (L 1 )](ClO 4 ) 2 (1 ClO4 ) complex (CCDC code ). 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) , N(2)-Ag-N(6)

2 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

3 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

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

5 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

6 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

7 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

8 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

9 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

10 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

11 Supplementary Figure 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

12 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

13 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

14 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

15 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

16 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

17 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

18 b) 18

19 c) 19

20 d) 20

21 Supplementary Figure 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

22 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

23 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

24 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

25 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

26 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

27 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 28

29 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

30 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

31 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

32 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

33 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 = K. ΔH = 19.3 ± 0.6 kcal/mol ΔS = ± 2 cal/mol K 33

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

81 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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

101 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

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

103 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

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

105 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

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

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

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

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

110 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

111 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 % 2 L 1-Br traces % % % % % % % % 18 d 1 1 (Tl(OTf)) 50% % 19 d 1 10 (Tl(OTf)) 58% % 20 d 0 10 (Tl(OTf)) 0% % 21 d L 1-I % % 22 d % % 23 d 1 1 (Tl(OTf)) 68% % 24 d 4 4 (Tl(OTf)) 78% a General conditions: [L 1-X] = 15 mm, [Ag I ] = mm, [additive] = 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

112 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

113 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 Compound 1 ClO4 Empirical formula C 15 H 24 Ag Cl 2 N 3 O 8 Formula weight Temperature, K 150(10) Wavelenght, Å Crystal system monoclinic Space group P21/n Unit cell dimensions a, Å (4) α, deg b, Å (5) β, deg (4) c, Å (8) γ, deg Volume, Å (14) Density (calculated), g cm Cell formula units_z 4 Absorption coefficient, mm Crystal size, mm 0.31 x 0.12 x 0.08 Reflections collected Independent reflections 5122 [R(int) = ] Final R indices [I<2σ(I)] α R1 = , wr2 = R indices (all data) R1 = , wr2 = / 2 [ F0 F ]/ F0 0 R c wr [ ( w( F0 Fc ) ) / ( wf )] 113

114 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 = ) TS-L 1 -Ag-F -ACN (G = ) L 1 -Ag I -F -ACN (G = )

115 L 1 -Ag III -Cl -ACN (G = ) TS-L 1 -Ag-Cl-ACN (G = ) L 1 -Ag I -Cl-ACN (G = )

116 L 1 -Ag III -Br -ACN (G = ) TS-L 1 -Ag-Br-ACN (G = ) L 1 -Ag I -Br -ACN (G = )

117 L 1 -Ag III -I -ACN (G = ) TS-L 1 -Ag-I-ACN (G = -1041,362100) L 1 -Ag I -I -ACN (G = )

118 L 5 -Ag III -F -ACN (G = ) TS-L 5 -Ag-F -ACN (G = ) L 5 -Ag I -F -ACN (G = )

119 L 1 -Ag III -p-no 2 phenol -ACN (G = ) TS-L 1 -Ag-p-NO 2 phenol -ACN (G = )

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