Skip to main content
SpringerLink
Log in

Highly efficient PdCu3 nanocatalysts for Suzuki–Miyaura reaction

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Suzuki–Miyaura reactions, involving the activation of carbon–halogen bonds, especially C–Cl bonds, have drawn widespread attention because of their huge industrial potential. However, these reactions are dependent on the development of highly active and stable catalysts. Herein, we developed a convenient one-pot wet route to synthesize Pd x Cu y bimetallic nanocrystals for the Suzuki–Miyaura reaction. By introducing Cu, an earth-abundant element, the catalytic activity was greatly enhanced while the amount of Pd required was reduced. Pd x Cu y nanocrystals of different compositions, including Pd3Cu, Pd2Cu, PdCu, PdCu2, and PdCu3, were successfully synthesized by tuning the Pd:Cu ratio. Their catalytic performance in Suzuki–Miyaura reactions between phenylboronic acid and halobenzenes (iodo-, bromo-, or chlorobenzene) showed that PdCu3 nanocatalyst demonstrated the best efficacy.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Marion, N.; Navarro, O.; Mei, J. G.; Stevens, E. D.; Scott, N. M.; Nolan, S. P. Modified (NHC)Pd(allyl)Cl (NHC = N-heterocyclic carbene) complexes for room-temperature Suzuki–Miyaura and Buchwald–Hartwig reactions. J. Am. Chem. Soc. 2006, 128, 4101–4111.

    Article  Google Scholar 

  2. Marion, N.; Nolan, S. P. Well-defined N-heterocyclic carbenes-palladium(II) precatalysts for cross-coupling reactions. Acc. Chem. Res. 2008, 41, 1440–1449.

    Article  Google Scholar 

  3. Schlummer, B.; Scholz, U. Palladium-catalyzed C–N and C–O coupling—A practical guide from an industrial vantage point. Adv. Synth. Catal. 2004, 346, 1599–1626.

    Article  Google Scholar 

  4. Alberico, D.; Scott, M. E.; Lautens, M. Aryl–aryl bond formation by transition-metal-catalyzed direct arylation. Chem. Rev. 2007, 107, 174–238.

    Article  Google Scholar 

  5. Barder, T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald, S. L. Catalysts for Suzuki–Miyaura coupling processes: Scope and studies of the effect of ligand structure. J. Am. Chem. Soc. 2005, 127, 4685–4696.

    Article  Google Scholar 

  6. Dupont, J.; de Souza, R. F.; Suarez, P. A. Z. Ionic liquid (molten salt) phase organometallic catalysis. Chem. Rev. 2002, 102, 3667–3691.

    Article  Google Scholar 

  7. Kotha, S.; Lahiri, K.; Kashinath, D. Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis. Tetrahedron 2002, 58, 9633–9695.

    Article  Google Scholar 

  8. Martin, R.; Buchwald, S. L. Palladium-catalyzed Suzuki–Miyaura cross-coupling reactions employing dialkylbiaryl phosphine ligands. Acc. Chem. Res. 2008, 41, 1461–1473.

    Article  Google Scholar 

  9. Wolfe, J. P.; Singer, R. A.; Yang, B. H.; Buchwald, S. L. Highly active palladium catalysts for Suzuki coupling reactions. J. Am. Chem. Soc. 1999, 121, 9550–9561.

    Article  Google Scholar 

  10. Jin, M.-J.; Lee, D.-H. A practical heterogeneous catalyst for the Suzuki, Sonogashira, and Stille coupling reactions of unreactive aryl chlorides. Angew. Chem., Int. Ed. 2010, 49, 1119–1122.

    Article  Google Scholar 

  11. Yuan, B. Z.; Pan, Y. Y.; Li, Y. W.; Yin, B. L.; Jiang, H. F. A highly active heterogeneous palladium catalyst for the Suzuki–Miyaura and ullmann coupling reactions of aryl chlorides in aqueous media. Angew. Chem., Int. Ed. 2010, 49, 4054–4058.

    Article  Google Scholar 

  12. Cui, J. B.; Li, Y. J.; Liu, L.; Chen, L.; Xu, J.; Ma, J. W.; Fang, G.; Zhu, E. B.; Wu, H.; Zhao, L. X. et al. Nearinfrared plasmonic-enhanced solar energy harvest for highly efficient photocatalytic reactions. Nano Lett. 2015, 15, 6295–6301.

    Article  Google Scholar 

  13. Zhang, L.; Hou, F.; Tan, Y. W. Shape-tailoring of CuPd nanocrystals for enhancement of electro-catalytic activity in oxygen reduction reaction. Chem. Commun. 2012, 48, 7152–7154.

    Article  Google Scholar 

  14. Jia, W.; Wu, Y. E.; Chen, Y. F.; He, D. S.; Li, J. P.; Wang, Y.; Wang, Z.; Zhu, W.; Chen, C.; Peng, Q. et al. Interfaceinduced formation of onion-like alloy nanocrystals by defects engineering. Nano Res. 2016, 9, 584–592.

    Article  Google Scholar 

  15. Long, R.; Wu, D.; Li, Y. P.; Bai, Y.; Wang, C. M.; Song, L.; Xiong, Y. J. Enhancing the catalytic efficiency of the Heck coupling reaction by forming 5 nm Pd octahedrons using kinetic control. Nano Res. 2015, 8, 2115–2123.

    Article  Google Scholar 

  16. Tang, S. H.; Chen, M.; Zheng, N. F. Multifunctional ultrasmall Pd nanosheets for enhanced near-infrared photothermal therapy and chemotherapy of cancer. Nano Res. 2015, 8, 165–174.

    Article  Google Scholar 

  17. Wang, Z.-J.; Lv, J.-J.; Feng, J.-J.; Li, N. B.; Xu, X. H.; Wang, A.-J.; Qiu, R. H. Enhanced catalytic performance of Pd-Pt nanodendrites for ligand-free Suzuki cross-coupling reactions. RSC Adv. 2015, 5, 28467–28473.

    Article  Google Scholar 

  18. Hou, R. J.; Ye, W. T.; Porosoff, M. D.; Chen, J. G.; Wang, T. F. Selective hydrogenation of 1,3-butadiene on Pd-Ni bimetallic catalyst: From model surfaces to supported catalysts. J. Catal. 2014, 316, 1–10.

    Article  Google Scholar 

  19. Ma, C.; Du, Y. Y.; Feng, J. T.; Cao, X. Z.; Yang, J.; Li, D. Q. Fabrication of supported PdAu nanoflower catalyst for partial hydrogenation of acetylene. J. Catal. 2014, 317, 263–271.

    Article  Google Scholar 

  20. Rong, H. P.; Cai, S. F.; Niu, Z. Q.; Li, Y. D. Compositiondependent catalytic activity of bimetallic nanocrystals: AgPd-catalyzed hydrodechlorination of 4-chlorophenol. ACS Catal. 2013, 3, 1560–1563.

    Article  Google Scholar 

  21. Yarulin, A.; Berguerand, C.; Yuranov, I.; Cardenas-Lizana, F.; Prokopyeva, I.; Kiwi-Minsker, L. Pt-Zn nanoparticles supported on porous polymeric matrix for selective 3-nitrostyrene hydrogenation. J. Catal. 2015, 321, 7–12.

    Article  Google Scholar 

  22. Anbarasan, P.; Schareina, T.; Beller, M. Recent developments and perspectives in palladium-catalyzed cyanation of aryl halides: Synthesis of benzonitriles. Chem. Soc. Rev. 2011, 40, 5049–5067.

    Article  Google Scholar 

  23. Fihri, A.; Bouhrara, M.; Nekoueishahraki, B.; Basset, J.-M.; Polshettiwar, V. Nanocatalysts for Suzuki cross-coupling reactions. Chem. Soc. Rev. 2011, 40, 5181–5203.

    Article  Google Scholar 

  24. Ishiyama, T.; Murata, M.; Miyaura, N. Palladium(0)-catalyzed cross-coupling reaction of alkoxydiboron with haloarenes: A direct procedure for arylboronic esters. J. Org. Chem. 1995, 60, 7508–7510.

    Article  Google Scholar 

  25. Molander, G. A.; Canturk, B. Organotrifluoroborates and monocoordinated palladium complexes as catalysts-a perfect combination for Suzuki–Miyaura coupling. Angew. Chem., Int. Ed. 2009, 48, 9240–9261.

    Article  Google Scholar 

  26. Chinchilla, R.; Nájera, C. The sonogashira reaction: A booming methodology in synthetic organic chemistry. Chem. Rev. 2007, 107, 874–922.

    Article  Google Scholar 

  27. Favier, I.; Madec, D.; Teuma, E.; Gomez, M. Palladium nanoparticles applied in organic synthesis as catalytic precursors. Curr. Org. Chem. 2011, 15, 3127–3174.

    Article  Google Scholar 

  28. Hassan, J.; Sévignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M. Aryl–aryl bond formation one century after the discovery of the ullmann reaction. Chem. Rev. 2002, 102, 1359–1469.

    Article  Google Scholar 

  29. Johansson Seechurn, C. C. C.; Kitching, M. O.; Colacot, T. J.; Snieckus, V. Palladium-catalyzed cross-coupling: A historical contextual perspective to the 2010 nobel prize. Angew. Chem., Int. Ed. 2012, 51, 5062–5085.

    Article  Google Scholar 

  30. Wang, F.; Li, C. H.; Chen, H. J.; Jiang, R. B.; Sun, L.-D.; Li, Q.; Wang, J. F.; Yu, J. C.; Yan, C.-H. Plasmonic harvesting of light energy for Suzuki coupling reactions. J. Am. Chem. Soc. 2013, 135, 5588–5601.

    Article  Google Scholar 

  31. Gu, J.; Zhang, Y. W.; Tao, F. Shape control of bimetallic nanocatalysts through well-designed colloidal chemistry approaches. Chem. Soc. Rev. 2012, 41, 8050–8065.

    Article  Google Scholar 

  32. Xi, P. X.; Cao, Y.; Yang, F. C.; Ma, C.; Chen, F. J.; Yu, S.; Wang, S.; Zeng, Z. Z.; Zhang, X. Facile synthesis of Pdbased bimetallic nanocrystals and their application as catalysts for methanol oxidation reaction. Nanoscale 2013, 5, 6124–6130.

    Article  Google Scholar 

  33. Huang, K.; Li, G.; Huang, W.-P.; Yu, D.-G.; Shi, Z.-J. Arylation of a-pivaloxyl ketones with arylboronic reagents via Ni-catalyzed sp3 C–O activation. Chem. Commun. 2011, 47, 7224–7226.

    Article  Google Scholar 

  34. Quasdorf, K. W.; Antoft-Finch, A.; Liu, P.; Silberstein, A. L.; Komaromi, A.; Blackburn, T.; Ramgren, S. D.; Houk, K. N.; Snieckus, V.; Garg, N. K. Suzuki–Miyaura cross-coupling of aryl carbamates and sulfamates: Experimental and computational studies. J. Am. Chem. Soc. 2011, 133, 6352–6363.

    Article  Google Scholar 

  35. Ramgren, S. D.; Hie, L.; Ye, Y. X.; Garg, N. K. Nickelcatalyzed Suzuki–Miyaura couplings in green solvents. Org. Lett. 2013, 15, 3950–3953.

    Article  Google Scholar 

  36. Mondal, P.; Salam, N.; Mondal, A.; Ghosh, K.; Tuhina, K.; Islam, S. M. A highly active recyclable gold-graphene nanocomposite material for oxidative esterification and Suzuki cross-coupling reactions in green pathway. J. Colloid Interface Sci. 2015, 459, 97–106.

    Article  Google Scholar 

  37. Zhang, S.; Chang, C. R.; Huang, Z. Q.; Ma, Y. Y.; Gao, W.; Li, J.; Qu, Y. Q. Visible-light-activated Suzuki–Miyaura coupling reactions of aryl chlorides over the multifunctional Pd/Au/porous nanorods of CeO2 catalysts. ACS Catal. 2015, 5, 6481–6488.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. State Key Laboratory of Chemical Resource Engineering, School of Science, Beijing University of Chemical Technology, Beijing, 100029, China

    Weiwei Shi, Xiaoqing Chen, Suying Xu, Jiabin Cui & Leyu Wang

Authors
  1. Weiwei Shi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiaoqing Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Suying Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jiabin Cui
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Leyu Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Leyu Wang.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Shi, W., Chen, X., Xu, S. et al. Highly efficient PdCu3 nanocatalysts for Suzuki–Miyaura reaction. Nano Res. 9, 2912–2920 (2016). https://doi.org/10.1007/s12274-016-1176-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-016-1176-9

Keywords

Search

Navigation