Theoretical and Experimental Studies on Reaction Mechanism for Aerobic Alcohol Oxidation by Supported Ruthenium Hydroxide Catalysts

  • Fumiya Nikaidou
    Department of Chemical System Engineering and Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
  • Hiroshi Ushiyama
    Department of Chemical System Engineering and Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
  • Kazuya Yamaguchi
    Department of Chemical System Engineering and Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
  • Koichi Yamashita
    Department of Chemical System Engineering and Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
  • Noritaka Mizuno
    Department of Chemical System Engineering and Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

書誌事項

公開日
2010-06-01
資源種別
journal article
DOI
  • 10.1021/jp101692j
公開者
American Chemical Society (ACS)

この論文をさがす

説明

The experimentally proposed reaction mechanism for the aerobic alcohol oxidation by supported ruthenium hydroxide catalysts (Ru(OH)x/support, support = TiO2 or Al2O3) is theoretically investigated by means of ab initio quantum chemistry calculations with model catalysts “Ru(OH)3(OH2)3” and “RuCl3(OH2)3” for Ru(OH)x/support and RuClx/support, respectively. The experimentally proposed alcoholate formation and β-hydride elimination steps can be verified. In the case of 2-butanol (as a model substrate), the calculated activation energy for the alcoholate formation step with Ru(OH)3(OH2)3 (27.7 kJ mol−1) is much smaller than that with RuCl3(OH2)3 (123.2 kJ mol−1), showing that the alcoholate formation with Ru(OH)x/support much more easily proceeds than that with RuClx/support. The Ru(OH)x/support catalysts possess both Lewis acid (Ru center) and Bronsted base (OH− species) sites on the same metal site. Therefore, the alcoholate formation step can be promoted by the “concerted activation” of an alcohol by the L...

収録刊行物

被引用文献 (5)*注記

もっと見る

参考文献 (44)*注記

もっと見る

関連プロジェクト

もっと見る

詳細情報 詳細情報について

問題の指摘

ページトップへ