TY - JOUR
T1 - Dual Lewis Acidic/Basic Pd0.5Ru0.5-Poly(N-vinyl-2-pyrrolidone) Alloyed Nanoparticle
T2 - Outstanding Catalytic Activity and Selectivity in Suzuki-Miyaura Cross-Coupling Reaction
AU - Kutubi, Md Shahajahan
AU - Sato, Katsutoshi
AU - Wada, Kenji
AU - Yamamoto, Tomokazu
AU - Matsumura, Syo
AU - Kusada, Kohei
AU - Kobayashi, Hirokazu
AU - Kitagawa, Hiroshi
AU - Nagaoka, Katsutoshi
N1 - Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2015/12/1
Y1 - 2015/12/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84954555872&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84954555872&partnerID=8YFLogxK
U2 - 10.1002/cctc.201500758
DO - 10.1002/cctc.201500758
M3 - Article
AN - SCOPUS:84954555872
SN - 1867-3880
VL - 7
SP - 3887
EP - 3894
JO - ChemCatChem
JF - ChemCatChem
IS - 23
ER -