| Project/Area Number |
08555214
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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 | 展開研究 |
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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 UNIVERSITY,Graduate School of Engineering, Professor, 工学研究科, 教授 (40026068)
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| Co-Investigator(Kenkyū-buntansha) |
FUENO Hiroyuki KYOTO UNIVERSITY,Graduate School of Engineering, Assistant, 工学研究科, 助手 (30212179)
TACHIBANA Akitomo KYOTO UNIVERSITY,Graduate School of Engineering, Professor, 工学研究科, 教授 (40135463)
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| Project Period (FY) |
1996 – 1998
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| Project Status |
Completed (Fiscal Year 1998)
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| Budget Amount *help |
¥12,700,000 (Direct Cost: ¥12,700,000)
Fiscal Year 1998: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1997: ¥4,400,000 (Direct Cost: ¥4,400,000)
Fiscal Year 1996: ¥7,100,000 (Direct Cost: ¥7,100,000)
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| Keywords | ab initio MO calculations / interaction orbitals / projected reactive orbitals / allyl borons / pi-allyl platinum complex / pi-allyl palladium complex / Lewis acidic hardness / 分子軌道計算 / 軌道解析 / エノキシシラン / プロトンスポンジ / 白金π-アリル錯体 / パラジウムπ-アリル錯体 / 触媒作用 / アノメリック効果 / 反応性理論 / 反応経路解析 / 活性反応中間体 / 軌道相互作用 / 軌道位相 / 軌道重なり / 立体選択 |
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| Research Abstract |
The physical properties and chemical activities of molecules and reaction intermediates are not determined by the stable structure of molecules, but by the local structures, such as the specific atoms and functional groups, in those species. In this study, we have investigated allyl boron compounds and have estimated, for the first time, theoretically the electron-accepting ability and Lewis acidic hardness of the boron center. These quantities have been shown to change markedly depending on the type of auxiliary. The theoretically estimated reactivity of allyl boron compounds toward aldehydes has been demonstrated to give an excellent agreement with the activation energies calculated accurately by the ab initio MO method and to agree well also with the experimental results. We have revealed in this study the factors that should control the reactivity of allyl boron compounds and have provided a new reactivity scale which can be utilized for the design of novel boron reagents.
We have s
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tudied next the nucleophilic substitutions of the allyl carbons in palladium and platinum complexes of 2-chloro-2-propenyl ethyl carbonate, utilizing molecular orbital calculations and the concept of orbital interactions. In the case of platinum complexes, the calculations have shown that the metallacyclobutane structure and the eta^22-coordinated structure are comparable in energy and exchange of ligands in the eta^22-coordinated structure is not facile. Accordingly, the nucleophilic substitution should occur at the allyl carbon to give an allylated compound. In contrast, the metallacyclobutane structure is less stable than the eta^22-coordinated structure in the palladium complex. Substitution reaction takes place in the eta^22-complex to give an alkene compound as the major product. The reaction takes place catalytically in this case. The relative stability of the metallacyclobutane structure and the eta^22-structure has been interpreted very clearly in terms of the phase and overlap of the interaction orbitals. Less
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