Regioselective Hydrosilylation of Olefins Catalyzed by Co-Iminobipyridine Complexes: The Role of Cyclohexyl Substituent on the Imino Nitrogen

DOI PDF 研究データあり 参考文献71件
  • Daisuke Taguchi
    Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585 , Japan
  • Katsuaki Kobayashi
    Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585 , Japan
  • Toshiyuki Moriuchi
    Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585 , Japan
  • Hiroshi Nakazawa
    Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585 , Japan

書誌事項

公開日
2020-08-09
権利情報
  • https://academic.oup.com/pages/standard-publication-reuse-rights
DOI
  • 10.1246/bcsj.20200043
公開者
Oxford University Press (OUP)

この論文をさがす

説明

<jats:title>Abstract</jats:title> <jats:p>Regioselective hydrosilylation of aliphatic olefins catalyzed by Co-iminobipyridine complexes, Co⟨R⟩, were investigated, where R indicates a substituent on the imino nitrogen in an iminobipyridine ligand (iminobypyridine = [2,2′-bpy]-6-C(Me)=N-R). Syntheses of two complexes, Co⟨Mes⟩ (Mes = 2,4,6-trimethylphenyl) and Co⟨Cy⟩ (Cy = cyclohexyl), and comparison of their catalytic activity for hydrosilylation of 1-octene with diphenylsilane revealed that the reaction system using Co⟨Mes⟩ produced a mixture of anti-Markovnikov and Markovnikov hydrosilylation products, whereas that using Co⟨Cy⟩ produced the anti-Markovnikov product selectively. Crystal structures of these complexes implied that a catalytically active species derived from Co⟨Cy⟩ has narrower active space for hydrosilylation than that from Co⟨Mes⟩. According to the Chalk-Harrod mechanism, there are two types of hydrosilylated products (anti-Markovnikov and Markovnikov products), which stem from the way of terminal olefin insertion into an M-H bond (that is 1,2- or 2,1-insertion). One of the intermediates derived from Co⟨Cy⟩ in the Chalk-Harrod mechanism has hydride and silyl ligands. In the step of olefin insertion into the Co-H bond, 1,2-insertion is more likely to occur from the steric point of view, leading to selective formation of the anti-Markovnikov product.</jats:p>

収録刊行物

参考文献 (71)*注記

もっと見る

関連研究データ

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