1. Flocculates of Au nanoparticles in catalysis NMSL – nanoAu and catalysis 4/16/2015B. Y. Wang, J. H. Chen1

2. Nanoparticle ： AuNS-L-Pd Goal –Catalytic reaction within nanoparticle flocculates Experiment –Cyclotrimerization of 3-hexyne in chloroform at r.t. 4/16/2015 B. Y. Wang, J. H. Chen2 Dispersed in DMSO Dispersed in CHCl 3 + DMSO 靜置 取出 上層 Sub-micron Flocculates

3. Results 4/16/2015B. Y. Wang, J. H. Chen3 (A)(B) (A) 157±23 nm Dispersed in DMSO Dispersed in CHCl 3 + DMSO Aging Upper Soln (C)(A) (B) (D)

4. Results 4/16/2015B. Y. Wang, J. H. Chen4 (A)(B) (C) (A)(B) Dispersed in DMSO Dispersed in CHCl 3 + DMSO (C)(A) (B) (D) Aging Upper Soln

5. TypesDiagramsTEM images A B C Catalysis of different types 4/16/2015B. Y. Wang, J. H. Chen5

6. Catalytic results 4/16/2015B. Y. Wang, J. H. Chen6 TypesPd mol Particle weight (mg) Reaction time (hr) Yield (%) B3x10 -6 -0.5>99 A3.92x10 -7 10.511.52 B3.92x10 -7 10.514.47 C4.02x10 -7 1.70.50 A0.92x10 -7 0.61.52.69 B0.92x10 -7 0.61.55.19 C1.07x10 -7 2.21.50 1 c.c. CDCl 3 ; 0.075 mmol reactant; R.T. ; Stir rate: 300 rpm

7. 4/16/2015Richard Wang7 樣品 Cat. MCat. mol% 觸媒 重量 (mg) 反應 時間 (min) 產率 (%) RS/ L-Pd: 轉速 (rpm) 備註 A3x10 -3 4-30>99-- A. 林玉雲學姐的論文 B.3.92x10 -7 mol Pd/mg C.1.54x10 -7 mol Pd/mg D.3,22x10 -7 mol Pd/mg E.1.67x10 -7 mol Pd/mg F.2.60x10 -7 mol Pd/mg G.2.21x10 -7 mol Pd/mg H.3.35x10 -7 mol Pd/mg CDCl 3 :1 ml ; 反應物 :0.075 mmol ; *CDCl 3 :686  l 反應物 :0.05 mmol ＃ CDCl 3 :500  l 反應物 :0.0375 mmol B(13)3.92x10 -4 0.5213014-300 C0.92x10 -4 0.120.6905.21.1300 D1.6x10 -4 0.210.50120001.6600 D1.19x10 -3 1.583.76003.21.61200 E1.67x10 -4 0.2217800-600 F6.24x10 -4 0.832.4072001.4600 F*3.00x10 -3 4.137.863001.4990 G3.01x10 -3 4.0113.7507.511200 G#G# 6.10x10 -3 8.1313.91207411200 H # (13)6.10x10 -3 8.139.160530.81200 1 (Liquid) 6.08x10 -3 8.1016.512001.81200 1. 1.84x10 -7 mol Pd/mg

8. 4/16/2015B. Y. Wang, J. H. Chen8 L L+L-Pd L+L-Pd+thiol L-Pd 8.2 8.6 507-Pd 毒化實驗

9. 4/16/2015B. Y. Wang, J. H. Chen9 攪拌前 攪拌後 8.2 8.6 Sample 1 攪拌前後光譜變化

10. 4/16/2015B. Y. Wang, J. H. Chen10 樣品 Cat M Cat. mol% 觸媒重量 (mg) 反應 時間 (hr) 產率 (%) RS/ L-Pd: 轉速 (rpm) 備註 Cyclotrimerization G.2.21x10 -7 mol Pd/mg F. 1.84x10 -7 mol Pd/mg G6.10x10 -3 8.1313.927411200 16.08x10 -3 8.1016.5201.81200 Heck reaction G1.33x10 -7 0.001330.61.5951600 11.29x10 -7 0.001290.71.5851.8600

11. 4/16/2015B. Y. Wang, J. H. Chen11 Sample G

12. 4/16/2015B. Y. Wang, J. H. Chen12 Sample 1

13. 反應系統 Heck reaction Reaction condition ： 115 o C for 1.5 hr 4/16/2015Richard Wang13 10 mmol 0.278 ml Bp: 182 o C; MW: 203; D: 1.823 g/ml 10 mmol 0.355 ml Bp: 160 o C; MW: 128; D: 0.899 g/ml Pd: 0.001 mol% NEt 3 0.375 ml Bp: 88.8 o C; 0.25 ml DMSO Need Pd 1x10 -7 mol

14. 反應系統 Cyclotrimerization Reaction condition ： r.t. for 0.5 hr 4/16/2015Richard Wang14 0.075 mmol 8.52  l Bp: 81 o C; MW: 82.14; D: 0.723 g/ml 1 ml CHCl 3 、 THF Pd: 4 mol% Need Pd 3x10 -6 mol

15. RAW DATA 4/16/2015B. Y. Wang, J. H. Chen15

16. A-1 4/16/2015B. Y. Wang, J. H. Chen16

17. B-1 4/16/2015B. Y. Wang, J. H. Chen17

18. A-2 4/16/2015B. Y. Wang, J. H. Chen18

19. B-2 4/16/2015B. Y. Wang, J. H. Chen19

20. C. AuNS-L-Pd

21. D. AuNS-L

22. D. AuNS-L-Pd

23. F. AuNS-L

24. F. AuNS-L-Pd

25. G. AuNS-L-Pd

26. H. AuNS-L

27. H. AuNS-L-Pd

28. 4/16/2015B. Y. Wang, J. H. Chen28 1. L-AuNS-L-Pd