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日期： 2013.7.15 學生：陳盈源 指導教授：于淑君 博士

Synthesis, Characterization and Catalytic Application of Aminodipyridylphosphine Oxide Palladium(II) Complex and Its Supported Form on Gold Nanoparticles. 日期： 2013.7.15 學生：陳盈源 指導教授：于淑君 博士. Types of Catalysts. Supported Catalysts. Concept ：

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日期： 2013.7.15 學生：陳盈源 指導教授：于淑君 博士

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  1. Synthesis, Characterization and Catalytic Application of Aminodipyridylphosphine Oxide Palladium(II) Complex and Its Supported Form on Gold Nanoparticles 日期：2013.7.15 學生：陳盈源 指導教授：于淑君 博士

  2. Types of Catalysts

  3. Supported Catalysts • Concept： • Increasing the Heterogeniety of the Homogeneous Catalyst Systems. • Combining Both Benefits of Homogeneous and Heterogeneous Systems.

  4. Hybrid Catalyst Design Gold nanoparticles (AuNPs) have been known not only to possess solid surfaces resembling the (1 1 1) surface of bulk gold but also to behave like soluble molecules for their dissolvability, precipitability, and redissolvability.

  5. Spacing Linker Bidentate chelate effect Phosphine ligand • Phosphines are electronically and sterically tunable. • Air sensitive  metal leaching • P-C, P-OR cleavage under high temperature. • Hazard waste • High cost

  6. The Catalytic Applications of Palladium(II) • Advantages： • Functional group tolerance • Exhibit higher TOF • Suitably stable against water or air. Diverse Catalytic Reactivity： • Oxidation of Alcohols • Allylation of Aldehydes • Strecker Reaction • N-vinylation of amides • Heck • Stille • Suzuki • Sonogashira • Buchwald-Hartwig • Tsuji-Trost • Negishi • Oxidation of Alkenes

  7. Enamides

  8. Application of Enamides

  9. Motivation • To study the immobilization of molecular Pd(II) complexes on the surfaces of AuNPs by using the covalent linkage via a specially designed bipyridine ligand as spacing linkers. • Palladium catalyses have several advantages including functional group tolerance, exhibit higher TOF, and are suitably stable to run the reactions without the exclusion of water or air. • Using bipyridine ligand to replace phosphine ligand in organomatallic catalysis. • AuNPs have been known not only to possess solid surfaces resembling the (1 1 1) surface of bulk gold but also to behave like soluble molecules for their dissolvability, precipitability, and redissolvability.

  10. Motivation • To design an easily recovered and effectively recycled AuNPs supported palladium(II) complex catalyst. • Because AuNPs are microwave conductor like bulk gold, we will apply microwave flash heating to replace conventional thermal heating.

  11. Synthesis of HO-C11-Ppy2-Pd

  12. 1H NMR Spectrum of HO-C11-Ppy2-Pd

  13. IR Spectrum of HO-C11-Ppy2-Pd HO-C11-Ppy2 HO-C11-Ppy2-Pd Pd(OAc)2 1614 cm-1` Nagaki, A.; Takabayashi, N.; Moriwaki, Y.; Yoshida, J.-i. Chemistry – A European Journal2012, 18, 11871.

  14. Synthesis of C4-Ppy2-Pd

  15. 1H NMR Spectrum of C4-Ppy2-Pd

  16. IR Spectrum of C4-Ppy2-Pd C4-Ppy2 C4-Ppy2-Pd Pd(OAc)2 1614 cm-1` Nagaki, A.; Takabayashi, N.; Moriwaki, Y.; Yoshida, J.-i. Chemistry – A European Journal2012, 18, 11871.

  17. Crystal Structure of C4-Ppy2-Pd

  18. Crystal Structure of C4-Ppy2-Pd Pd 0.0461 Å N1 N2 O2 O4

  19. Synthesis of RS-Au-L-Pd

  20. Hostetler, M. J.; Templeton, A. C.; Murray, R. W. Langmuir1999, 15, 3782.

  21. 1H NMR Spectrum of RS-Au-L-Pd

  22. IR Spectrum of RS-Au-L-Pd RS-Au-L RS-Au-L-Pd

  23. EDS and TEM Image of RS-Au-L-Pd 1.675  0.3164 nm

  24. Reaction Conditions Screening

  25. Reaction Conditions Screening

  26. Reaction Conditions Screening

  27. Reaction Conditions Screening

  28. Reaction Conditions Screening

  29. Catalytic N-Vinylation of amides by Pd Catalyst

  30. Electronic Effect ?

  31. Recyclability of Catalyst RS-Au-L-Pd < 0.16  metal leaching

  32. Catalyst Recycling Efficiency

  33. Reaction Conditions Screening under Microwave

  34. Reaction Conditions Screening under Microwave

  35. Reaction Conditions Screening under Microwave

  36. Microwave Assisted Pd-Catalyzed N-Vinylation of amides

  37. Microwave Assisted Pd-Catalyzed N-Vinylation of amides

  38. Mechanism of Enamide Formation Xu, J.; Fu, Y.; Xiao, B.; Gong, T.; Guo, Q., Tetrahedron Letters 2010,51 (41), 5476-5479.

  39. Conclusions • We have developed a mild and efficient protocol for the Pd-catalyzed N-vinylation of amides with vinyl acetate. • The AuNPs supported Pd(II) complex catalyst not only provide comparable reactivity with its unbound form, but also offer excellent catalyst recyclability. • Further acceleration of the Pd(II) catalyzed N-vinylation was achieved under microwave irradiation conditions.

  40. 非傳統 Staudinger 反應

  41. AuNPs of Influence

  42. Reaction Conditions Screening under Microwave

  43. HO-C11-Ppy2-Pd HO-C11-Ppy2-Pd 65oC 2 hr

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