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Analyzes and Designs of Local Electronic Structures of Molecules and Chemical Reactions

Research Project

Project/Area Number 08305034
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field 工業物理化学
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

FUJIMOTO Hiroshi  Kyoto Univ., Engineering, Professor, 工学研究科, 教授 (40026068)

Co-Investigator(Kenkyū-buntansha) YAMABE Sinichi  Nara Univ., of Education, Chemistry, Professor, 教育学部, 教授 (00109117)
TOMODA Syuji  Tokyo Univ., Life and Environmental Sciences, Professor, 総合文化研究科, 教授 (30092282)
SYUDO Koichi  Tokyo Univ., Pharmaceutical Sciences, Professor, 薬学系研究科, 教授 (50012612)
SAKAKI Shigeyoshi  Kumamoto Univ., Engineering, Professor, 工学部, 教授 (20094013)
INAGAKI Satoshi  Gifu Univ., Engineering, Professor, 工学部, 教授 (10108061)
Project Period (FY) 1996 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥7,100,000 (Direct Cost: ¥7,100,000)
Fiscal Year 1997: ¥2,600,000 (Direct Cost: ¥2,600,000)
Fiscal Year 1996: ¥4,500,000 (Direct Cost: ¥4,500,000)
Keywordsmolecular orbital theory / electronic structure theory / reaction intermediates / transition structures / chemical reactivities / facial selectivities / optical activity / metal complexes / 電子構造 / 軌道相互作用 / 反応性評価 / キラリティー / 付加環化反応
Research Abstract

The purpose of this research is to make the theories more sophisticated and develop further to find out new principles in chemistry of general use through discussions and intimate cooperation between experimental chemists and theoreticians. The results so far obtained are summarized as follows. 1. By introducing a modification into the Hartree-Fock MO theory, the physical significance and the additivity of the pi electronic energy have been examined. 2. By applying the perturbation theory, the deformation of the highest occupied MO of cyclopentadiene has been clarified. The facial selectivity in cycloaddition has been discussed in terms of the shape of the orbital. 3. The mechanism of solvolysis in beta-substituted iodonium salts has been investigated. 4. The paths for the rearrangement of the square planar platinum (II) and related complexes have been studied by applying the density functional theory. In addition to the energy and structure calculations, orbital interactions by applying the Walsh diagram have indicated that some ligands chosen appropriately will provide stable tetrahedral Pt (II) and Pd (II) complexes that have not been found so far. 5. By taking reductive eliminations and activations of sp^3 C-H bonds as examples, ab initio Mo calculations have been demonstrated to be very useful in disclosing the molecular mechanisms of chemical reactions. 6. Sulfur complexes of molybdenum and tungsten having pentamethylcyclopentadienyl ligands have been synthesized and their clusters and stabilities have been studied from an electronic energy viewpoint. 7. Octahydro-4,4'-biphenanthrylidenes having twisted pi electron systems give optically active enantiomers. The stereochemistry of those enantiomers determined by theoretical calculations have been proved to be correct by experimental studies.

Report

(3 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] H.Ichikawa, H.Kogawa: "Relationship between the π-Electron Distribution and the Symmetry of Cyclic C_6H_6 Systems" Bulletin of the Chemical Society of Japan. 70. 1805-1807 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Sakaki, K.Takeuchi, M.Sugimoto, H.Kurosawa: "Geometries,Bonding Nature and Relative Stabilities of Dinuclear Palladium (I) π-allyl and Mononuclear Palladium (II) π-AllyI Complexes. A Theoretical Study" Organometallics. 16. 2995-3003 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] M.Tsuji, T.Ohwada, K.Shudo: "A CyclopropyI Group Shows Reverse Facial Selectivity Depending on the Bicyclic Ring System" Tetrahedron Letters. 38. 6693-6696 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Kawaguchi, K.Yamada, S.Ohnishi, K.Tatsumi: "Construction of a Cyclic Tricubane Cluster [Cp^*_2Mo_2Fe_2S_4] _3 (μ-S_4)_3 from the Mo_2Fe_2S_4 Single Cubance Component" Journal of the American Chemical Society. 119. 10871-10872 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Senju, S.Tomoda: "Quantitative Analyses of Cieplak vs.Felkin-Anh Effects in Hydride Reduction of Cyclohexanone" Chemistry Letters. 1997. 431-432 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Yamabe, T.Ishikawa: "Hydrogen-Bond Networks for Hydrolyses of Anhydrides" Journal of Organic Chemistry. 62. 7049-7053 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Ichikawa, H.Kogawa: "Relationship between the pi-Electron Distribution and the Symmetry of Cyclic C_6H_6 Systems" Bulletin of the Chemical Society of Japan. 70. 1805-1807 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Sakaki, K.Takeuchi, M.Sugimoto, H.Kurosawa: "Geometries, Bonding Nature and Relative Stabilities of Dinuclear Palladium (I) pi-allyl and Mononuclear Palladium (II) pi-Allyl Complexes. A Theoretical Study" Organometallics. 16. 2995-3003 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] M.Tsuji, T.Ohwada, K.Shudo: "A Cyclopropyl Group Shows Reverse Facial Selectivity Depending on the Bicyclic Ring System" Tetrahedron Letters. 38. 6693-6696 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Kawaguchi, K.Yamada, S.Ohnishi, K.Tatsumi: "Construction of a Cyclic Tricubane Cluster [Cp^<**>_2Mo_2Fe_2S_4]_3(mu-S_4)_3 from the Mo_2Fe_2S_4 Single Cubane Component" Journale of the American Chemical Society. 119. 10871-10872 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Senju, S.Tomoda: "Quantitative Analyzes of Cieplak vs.Felkin-Anh Effects in Hydride Reduction of Cyclohexanone" Chemistry Letters. 1997. 431-432 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Yamabe, T.Ishikawa: "Hydrogen-Bond Networks for Hydrolyses of Anhydrides" Journal of Organic Chemistry. 62. 7049-7053 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Ichikawa, H.Kogawa: "Relationship between the π-Electron Distribution and the Symmetry of Cyclic C_6H_6 Systems" Bulletin of the Chemical Society of Japan. 70. 1805-1807 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Sakaki, K.Takeuchi, M.Sugimoto, H.Kurosawa: "Geometries,Bonding Nature and Relative Stabilities of Dinuclear Palladium (I) π-allyl and Mononuclear Palladium (II) π-Allyl Complexes. A Theoretical Study" Organometallics. 16. 2995-3003 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] M.Tsuji, T.Ohwada, K.Shudo: "A Cyclopropyl Group Shows Reverse Facial Selectivity Depending on the Bicyclic Ring System" Tetrahedron Letters. 38. 6693-6696 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Kawaguchi, K.Yamada, S.Ohnishi, K.Tatsumi: "Construction of a Cyclic Tricubane Cluster 〔Cp^*_2Mo_2Fe_2S_4〕_3(μ-S_4)_3 from the Mo_2Fe_2S_4 Single Cubane Component" Journal of the American Chemical Society. 119. 10871-10872 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Senju, S.Tomoda: "Quantitative Analyses of Cieplak vs.Felkin-Anh Effects in Hydride Reduction of Cyclohezanone" Chemistry Letters. 1997. 431-432 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Yamabe, T.Ishikawa: "Hydrogen-Bond Networks for Hydrolyses of Anhydrides" Journal of Organic Chemistry. 62. 7049-7053 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] M.Yagi,S.Tokita,K.Nagoshi,I.Ogino,M.Kaneko: "Activity Analysis of a Water Oxidation Catalyst Immobilized in a Polymer Membrane" Journal of the Chemical Society Faraday Transactions. 92. 2457-2461 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Inagaki,T.Kakefu,T.Yamamoto: "Geminal Delocalization of σ-Electrons and Inverted Configurations of the Bridgehead Carbons in Bicyclo[1.1.0]butane Fragments" Journal of Physical Chemistry. 100. 9615-9618 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Iwaoka,R.Tomoda: "Nature of the Intramolecular Se・・・N Non-Bonded Interaction of 2-Selenobenzylamine Derivatives. An Experimental Evaluation by H-1,C-13,Se-77 and,N-15 NMR Spectroscopy" Journal of the American Chemical Society. 118. 8077-8084 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] I.Okamoto,T.Ohwada,K.Shudo: "Orbital Unsymmetrization Affects Facial Selectivities of Diels-Alder Dienophiles" Journal of Organic Chmistry. 61. 3155-3166 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Sakaki,H.Satoh,H.Shono,Y.Ujino: "Ab Initio MO Study of the Geometry,η^3【tautomer】η^1 Conversion,and Reductive Elimination of a Palladium(II) η^3-Allyl Hydride Complex and Its Platinum(II) Analogue" Organometallics. 15. 1713-1720 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Yamabe,T.Dai: "Ketene Is a Dienophile for [4+2](Diels-Alder)Reactions across Its C=O Bond." Journal of the American Chemical Society. 118. 6518-6519 (1996)

    • Related Report
      1996 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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