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Regio- and Chemoselective Hydrogenation of Dienes to Monoenes Governed by a Well-Structured Bimetallic Surface.

Unprecedented surface chemistry, governed by specific atomic arrangements and the steric effect of ordered alloys, is reported. Rh-based ordered alloys supported on SiO (RhM/SiO, M = Bi, Cu, Fe, Ga, In, Pb, Sn, and Zn) were prepared and tested as catalysts for selective hydrogenation of trans-1,4-he...

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Published in:Journal of the American Chemical Society Vol. 139; no. 50; pp. 18231 - 18240
Main Authors: Masayoshi Miyazaki, Shinya Furukawa, Takayuki Komatsu
Format: Article
Published: American Chemical Society 12/20/2017
Subjects:
Surface chemistry
Hydrogenation
Regioselectivity (Chemistry)
Rhodium alloys
Density functional theory
Online Access:View this record in EBSCOhost
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        00027863
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      issn: 00027863
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      dt: 12/20/2017
      vid: 139
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      pub: American Chemical Society
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        127093240
        10.1021/jacs.7b08792
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        atl: Regio- and Chemoselective Hydrogenation of Dienes to Monoenes Governed by a Well-Structured Bimetallic Surface.
      aug:
        au:
          Masayoshi Miyazaki
          Shinya Furukawa
          Takayuki Komatsu
        affil:
          Department of Chemistry, School of Science, Tokyo Institute of Technology, 2-12-1-E1-10 Ookayama, Meguro-ku, Tokyo 152-8551, Japan
          Institute for Catalysis, Hokkaido University, N10 W21, Kita-ku, Sapporo 001-0021, Japan
          ESICB, Kyoto University, Nishikyo-ku, Kyoto 519-5510, Japan
      su:
        Surface chemistry
        Hydrogenation
        Regioselectivity (Chemistry)
        Rhodium alloys
        Density functional theory
      sug:
        subj:
          Surface chemistry
          Hydrogenation
          Regioselectivity (Chemistry)
          Rhodium alloys
          Density functional theory
      ab: Unprecedented surface chemistry, governed by specific atomic arrangements and the steric effect of ordered alloys, is reported. Rh-based ordered alloys supported on SiO (RhM/SiO, M = Bi, Cu, Fe, Ga, In, Pb, Sn, and Zn) were prepared and tested as catalysts for selective hydrogenation of trans-1,4-hexadiene to trans-2-hexene. RhBi/SiO exhibited excellent regioselectivity for the terminal C═C bond and chemoselective hydrogenation to the monoene, not to the overhydrogenated alkane, resulting in a high trans-2-hexene yield. Various asymmetric dienes, including terpenoids, were converted into the corresponding inner monoenes in high yields. This is the first example of a regio- and chemoselective hydrogenation of dienes using heterogeneous catalysts. Kinetic studies and density functional theory calculations revealed the origin of the high selectivity: (1) one-dimensionally aligned Rh arrays geometrically limit hydrogen diffusion and attack to alkenyl carbons from one direction and (2) adsorption of the inner C═C moiety to Rh is inhibited by steric repulsion from the large Bi atoms. The combination of these effects preferentially hydrogenates the terminal C═C bond and prevents overhydrogenation to the alkane.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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          year: 2017
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