Research on Chemical Intermediates

, Volume 41, Issue 12, pp 9575–9586 | Cite as

Phosphine-stabilized, oxide-supported rhodium catalysts for highly efficient silylative coupling reactions

  • Shinji Tsukada
  • Kenji Wada
  • Hiroki Miura
  • Saburo Hosokawa
  • Ryu Abe
  • Masashi Inoue
Article
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Abstract

Oxide-supported rhodium catalysts with excellent activity in silylative coupling reactions have been developed. Reductive pretreatment of the catalysts in the presence of 0.5 equiv triphenylphosphine under a hydrogen atmosphere enhanced and stabilized the catalytic activity. Of the catalysts examined, ceria-supported rhodium had the highest activity in the homo-coupling of vinylsilanes to bis(silyl)ethenes at 170 °C. A zirconia-supported catalyst selectively gave E-1-aryl-2-silylethenes by cross-coupling of vinylsilanes with styrenes at 130 °C, and a high turnover frequency of >8200 h−1 was achieved at 170 °C. Spectroscopic studies revealed that well-dispersed surface rhodium(I) species predominantly formed on ceria or zirconia were transformed into rhodium hydride species, which are believed to be responsible for the high activity. These catalysts were recyclable without loss of activity, and leaching of rhodium species from the catalysts was not observed.

Keywords

Supported catalyst Rhodium Ceria Zirconia Phosphine-modification Vinylsilane Styrenes Silylative coupling 
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Notes

Acknowledgements

This work was supported by a Grant-in-Aid for Scientific Research (no. 24360333) from the Ministry of Education, Sports, Culture, Science and Technology, Japan and the JST ALCA program.

Supplementary material

11164_2015_1983_MOESM1_ESM.pdf (435 kb)
Characterization of the supported rhodium catalysts and experimental details (PDF 435 kb)

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Copyright information

© Springer Science+Business Media Dordrecht 2015

Authors and Affiliations

  • Shinji Tsukada
    • 1
  • Kenji Wada
    • 2
  • Hiroki Miura
    • 1
    • 3
    • 4
  • Saburo Hosokawa
    • 4
  • Ryu Abe
    • 1
  • Masashi Inoue
    • 1
  1. 1.Department of Energy and Hydrocarbon Chemistry, Graduate School of EngineeringKyoto UniversityKyotoJapan
  2. 2.Department of Chemistry for Medicine, Graduate School of MedicineKagawa UniversityKita-gunJapan
  3. 3.Department of Urban Environmental SciencesTokyo Metropolitan UniversityHachioji-shiJapan
  4. 4.Elements Strategy Initiative for Catalysts and Batteries (ESICB)Kyoto UniversityKyotoJapan

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