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Asymmetric Syntheses by Use of Intercalation of Multi-nuclear Chiral Metal Complexes into a Clay

Research Project

Project/Area Number 05453048
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 機能・物性・材料
Research InstitutionHokkaido University

Principal Investigator

YAMAGISHI Akihiko  Hokkaido University., Faculty of Science, professor, 理学部, 教授 (70001865)

Co-Investigator(Kenkyū-buntansha) ARAMATA Akiko  Hokkaido University., Research Center for Catalysis, Associate Professor, 触媒化学研究センター, 助教授 (80001717)
TAKAHASHI Masayuki  Hokkaido University., Faculuty of Science, Instructor, 理学部, 助手 (50241295)
Project Period (FY) 1993 – 1994
Project Status Completed (Fiscal Year 1994)
Budget Amount *help
¥5,300,000 (Direct Cost: ¥5,300,000)
Fiscal Year 1994: ¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1993: ¥3,000,000 (Direct Cost: ¥3,000,000)
KeywordsClay minerals / Asymmetric Catalysis / Induced CD / Electric dichroism / 不斉場 / 多核錯体
Research Abstract

The purpose of the present project is to develop of a new catalytic system for asymmetric syntheses by use of clay minerals. Our approach is to synthesize an intercalation compound of a clay with optically active metal complexes. The chiral metal complexes are expected to form a chiral reaction space within the clay layrs. If the metal complexes are capable to catalyze some reactions (e.g.oxidation, reduction, hydrogenation etc), they will achieve asymmetric syntheses with high efficiency.
As a result, we have established the following reaction systems involving a clay. Two kinds of metal complexes were coadsorbed by a colloidally dispersed clay ; [Fe (terpy) ] ^<3+> terpy=2,2', 2''- terpyridyl) and [Ni (phen) _3]^<2+> (phen=1,10-phenanthroline). The Fe complex is capable of oxidizing an organic substance such as ascorbic acid or cystein, but it has no optical activity. The Ni complex has no redox properties but it is chiral due to the helical nature of three phenanthroline ligands. It was expected that the oxidation by the Fe complex proceeded under the chiral circumstances of the Ni complex when these two kinds of complexes were on the same clay surface. This was realized by comparing the oxidation rates of D- or L-cystein in the presence of a colloidally dispersed clay absorbing [Fe (terpy) ] ^<3+> and DELTA- [Ni (phen) _3] ^<2+>. L-Cystein was found to be oxidized at the higher rate than D-cystein, showing the stereoselectivity in the reaction.
The structures of the present clay catalysis have been investigated with various spectroscopic methods : the measurements of induced CD,the electric dichroism spectra and the observations with atomic force microscopy.

Report

(3 results)
  • 1994 Annual Research Report   Final Research Report Summary
  • 1993 Annual Research Report
  • Research Products

    (20 results)

All Other

All Publications (20 results)

  • [Publications] 山岸晧彦,佐藤久子: "粘土表面による分子認識-理論的アプローチ" 表面. 31. 375-387 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] 山岸,チヨウナイン,後藤康友,谷口昌宏,高橋正行: "Formation of Optically Active 〔Ru(bpy)_2Cl_2〕by Photodissociation of 〔Ru(bpy)_3〕Cl_2 in CH_2Cl_2" Journal of Chemical Society,Dalton Trans.2085-2089 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] 山岸晧彦,堀田裕司: "粘土薄膜の電極修飾剤への応用" 粘土科学. 33. 233-245 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] 山岸晧彦,高橋正行,谷口昌宏: "Electric dichroism studies on adsorption of 〔Ru(DMOPY)_3〕^<2+> by a Colloidal clay" Journal of Physical Chemistry. 98. 7555-7561 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] 山岸晧彦: "粘土面でのキラル識別" 日本化学会誌. 10. 853-866 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] 姚建,嶋津克明,山岸晧彦: "Mass transport on a clay modified electrode as studied by quartz crystal microbalance method" Chemistry Letters. 161-161 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] A.Yamagishi, H.Sato: "Molecular Recognition on a Clay Surface : Theoretical Approrch" Hyomen. 31. 375-387 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] A.Yamagishi, K.Naing, Y.Goto, M.Taniguchi & M.Takahashi: "Formation of Optically Active [Ru (bpy) _2Cl_2] by Photodissociation of [Ru (bpy) _3]Cl_2 in CH_2Cl_2" J.Chem.Soc., Dalton Trans.2085-2089 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] A.Yamagishi, Y.Hotta: "Application of Clay Thin films for Electrode Modifiers" Nendo Kagaku. 33. 233-245 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] A.Yamagishi, M.Takahashi & M.Taniguchi: "Electin Dichroism Studies on Adsorption of [Ru (DMOPY) _3] ^<2+> by a colloidal Clay" J.Phys.Chem.98. 7555-7561 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] A.Yamagishi: "Chiral Recogintion by a Clay Surface" Nihon Kagaku kaishi. 10. 853-866 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Y.Ken, K.Shimazu & A.Yamagishi: "Mass Transport on a Clay Modified Electrode as studied by Quartz Crystal Microbalance Method" Chem.Lett.161-161 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] 山岸晧彦、堀田裕司: "粘土薄膜の電極修飾剤への応用" 粘土科学. 33. 233-245 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 山岸晧彦: "粘土面でのキラル識別" 日本化学会誌. 10. 853-866 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 姚建、嶋津克明、山岸晧彦: "Mass Transport on a Clay Modified Electrode as Studied by Quarte Microbalance Method" Chemistry Letters. 161-161 (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Kaneyoshi,A.Yamagishi & A.Aramata: "Adsorption & Spectroscopic Studies on Interactions of Co(14) Chelates with Clays" Clays and Clay Minerals. 41. 1-6 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Inukai,Y.Hotta,M.Taniguchi,S.Tomura,A.Yamagishi: "Formation of a Clay Monolayer at Air-Water Interface" Journal of chemical Society,Chemical Communication. (印刷中). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] 山岸晧彦・佐藤久子: "粘土表面による分子認識-理論的アプローチ" 表面. 31. 375-387 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] 山岸晧彦: "粘土層間の分子形状認識機能" SMECTITE(スメクタイト). 3. 19-30 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Akihiko Yamagishi Ed.by Kenzi Tamaru: "Dynamic Processes on Solid Surfaces" Plenum Publishing Corporation,London,UK, 340 (1993)

    • Related Report
      1993 Annual Research Report

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Published: 1993-04-01   Modified: 2016-04-21  

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