Au25 Clusters as Electron-Transfer Catalysts Induced the Intramolecular Cascade Reaction of 2-nitrobenzonitrile

Hanbao Chong, Peng Li*, Shuxin Wang, Fangyu Fu, Ji Xiang, Manzhou Zhu*, Yadong Li*

Content

1. UV-vis spectrum of Au25(SCH2CH2Ph)18-

2. MALDI-TOF-MS of Au25(SCH2CH2Ph)18-

3. Cyclic voltammograms data of 2-nitrobenzonitrile and Au25(SCH2CH2Ph)18-

4. ESR spectrum of reaction mixture

5. Mass spectrum of 2-aminobenzamide

6. Mass spectrum of D-marked 2-aminobenzamide

7. Figure S6. TEM image of Au NPs

8. Proposed possible paths toward the reaction process

9. UV-vis spectrum of recovered Au25(SCH2CH2Ph)18 after reaction completed

10. MALDI-TOF-MS of Au25(SCH2CH2Ph)18 after reaction completed

11. Spectroscopic characterization of products

12. NMR spectra of products

Figure S1. UV-vis spectrum of Au25(SCH2CH2Ph)18-

Figure S2. MALDI-TOF MS of Au25(SCH2CH2Ph)18-

Table S1. Cyclic Voltammetry Results of 2-nitrobenzonitrile, 4-nitrobenzonitrile, nitrobenzene and Au25(SC2H4Ph)18-TOA+

/V / /V / V / /V
2-nitrobenzonitrile0/-1 / 1.087 / -0.144 / 1.231 / 0.093
Au250/-1 / 0.033 / -0.038 / 0.071 / -0.030

Figure S3. ESR signals of the reaction mixture of Au25- 1a and NaBH4. (1a FW = 148.12, 0.8 mg dissolved in 0.55 mL THF) added to the solution of Au25- clusters (FW =7860.6, 3 mg in 0.55 mL THF) before 5 mg of NaBH4 was added.

Figure S4. Mass spectrum of 2-aminobenzamide

Figure S5. Mass spectrum of D-marked 2-aminobenzamide

Figure S6. TEM image of Au NPs

Figure S7. Proposed possible paths toward the reaction process.

Figure S8. UV-vis spectrum of recovered Au25(SCH2CH2Ph)18 after reaction completed.

Figure S9. MALDI-TOF of Au25(SCH2CH2Ph)18 after reaction completed.

Spectroscopic characterization of products

2-aminobenzamide

1H NMR (400 MHz, [D1] CDCl3, TMS ):δ= 5.67 (s, 2H, NH2), 5.90 (s, 2H, NH2), 6.62-6.69 (m, 2H, CH), 7.21-7.26 (dd, 3J (H,H)= 7.21, 14.44 Hz, 1H, CH), 7.35-7.37 (d, 3J (H,H)= 7.92 Hz, 1H, CH); 13C NMR (100 MHz, [D1] CDCl3, TMS): δ= 171.71, 149.44, 133.01, 128.02, 117.45, 116.42, 114.02 ppm.

4-aminobenzonitrile

1H NMR (400 MHz, [D1] CDCl3, TMS ):δ= 7.41-7.39 (d, 3J (H,H)= 8.6 Hz, 2H, CH), 6.66-6.64 (d, 3J (H,H) = 8.6 Hz, 2H, CH), 4.21 ppm (s, 2H); 13C NMR (100 MHz, [D1] CDCl3, TMS): δ= 150.51, 133.81, 120.20, 114.45, 100.06 ppm.

(Z)-1,2-diphenyldiazene oxide

1H NMR (400 MHz, [D1]CDCl3, TMS ):δ=7.38 (t, 3J(H,H)=7.36Hz, 1H, CH), 7.52 (m, 5H, CH), 8.17 (m, 2H, CH), 8.30 ppm (m, 2H, CH); 13C NMR (100 MHz, [D1]CDCl3, TMS ): δ=144.04, 131.58, 129.60, 128.80, 128.70, 125.53, 122.36 ppm.

4-(hydroxyamino)benzonitrile

1H NMR (400 MHz, [D6]DMSO, TMS ):δ=8.76 (s, 1H, OH), 7.56 (d, 3J(H,H) = 8.5 Hz, 2H, CH), 6.78 ppm (d, 3J(H,H) = 8.5 Hz, 2H, CH); 13C NMR (100 MHz, [D6]DMSO, TMS ): 152.65, 133.69, 119.97, 111.36, 98.86 ppm.

NMR spectra of products