Dual Lewis Acidic/Basic Pd0.5Ru0.5-Poly(N-vinyl-2-pyrrolidone) Alloyed Nanoparticle: Outstanding Catalytic Activity and Selectivity in Suzuki-Miyaura Cross-Coupling Reaction

Md Shahajahan Kutubi, Katsutoshi Sato, Kenji Wada, Tomokazu Yamamoto, Syo Matsumura, Kohei Kusada, Hirokazu Kobayashi, Hiroshi Kitagawa, Katsutoshi Nagaoka

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18 Citations (Scopus)

Abstract

This article anticipates the development of dual Lewis acidic/basic alloyed nanoparticle (NP) of poly(N-vinyl-2-pyrrolidone)-stabilized Pd0.5Ru0.5 solid solution, revealing equivalent Pdδ+ and Ruδ- on the NP surface. This unsupported NP disclosed excellent catalytic efficiency with high turnover frequency, 15 000 h-1 in Suzuki-Miyaura cross-coupling under notable drop of both Pd loading (0.08 mol %) and time (5 min) in air, attributed for its bifunctional acidic/basic modes. The bifunctional modes exposed the most interesting new reaction mechanism ascribed by the inductive effects of p-substituents in arylboronic acid, accelerated reactivity by electron-withdrawing group, revealing an opposite reactivity trend relative to other Pd-based catalysts. Besides, the significant drops of Pd loading and reaction time impeded the metal leaching associated with no changes in NP surface composition/structure after the 3rd cycle (>99 % efficiency), revealing a line-up for this NP in the environmental sustainability. Opposing charges, working together: Bifunctional Lewis acidic/basic Pdδ+Ruδ-(1:1) solid-solution nanoparticles disclose a remarkable catalytic efficiency in the Suzuki-Miyaura reaction at very low Pd loading and short reaction time in air. It reveals enhanced reactivity by the electron-withdrawing groups on arylboronic acids, resulting negatively charged aromatic ring in the transition state, which is a clear controversy to the conventional Pd catalysis.

Original languageEnglish
Pages (from-to)3887-3894
Number of pages8
JournalChemCatChem
Volume7
Issue number23
DOIs
Publication statusPublished - Dec 1 2015

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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