1997 Fiscal Year Final Research Report Summary
Analyzes and Designs of Local Electronic Structures of Molecules and Chemical Reactions
| Project/Area Number |
08305034
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
工業物理化学
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| Research Institution | KYOTO UNIVERSITY |
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Principal Investigator |
FUJIMOTO Hiroshi Kyoto Univ., Engineering, Professor, 工学研究科, 教授 (40026068)
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| 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)
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| Project Period (FY) |
1996 – 1997
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| Keywords | molecular orbital theory / electronic structure theory / reaction intermediates / transition structures / chemical reactivities / facial selectivities / optical activity / metal complexes |
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| 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.
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