| Project/Area Number |
18350005
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Physical chemistry
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| Research Institution | Kyoto University |
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Principal Investigator |
SAKAKI Shigeyoshi Kyoto University, Graduate School of Engineering, Professor (20094013)
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| Co-Investigator(Kenkyū-buntansha) |
SATO Hirofumi Kyoto University, Graduate School of Engineering, Associate Professor (70290905)
NAKAO Yoshihide Kyoto University, Graduate School of Engineering, Research Associate (40362462)
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| Project Period (FY) |
2006 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥15,080,000 (Direct Cost: ¥14,000,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2007: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2006: ¥10,400,000 (Direct Cost: ¥10,400,000)
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| Keywords | Electronic Structure Theory / Transition Metal Complexes / Reaction Mechanism / Bonding Nature / Structure / Electron correlation effects / Shift operator / Physical properties / 電子状態理論 / スピンクロスオーバー / 反応機構 / 結合性 / 構造 / 電子相関効果 / 反応制御 / 機能制御 |
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| Research Abstract |
Theoretical studies of transition metal complexes bearing flexible electronic structure were carried out with modern electronic structure theories in this project.
Oxidative addition of σ-bond to nickel(0) complex was theoretically investigated with density functional theory and post-Hartree-Fock method. Though the density functional theory did not present quantitatively correct features of the reaction, highly sophisticated post-Hartree-Fock method presented correct results when high quality basis sets were employed.
To perform post-Hartree-Fock calculation of real complexes, we newly proposed shift operator with which we can incorporate electronic effects of bulky substituent. This shift operator is very effective ; actually, we succeeded to reproduce the electronic structure of large metal complexes with this shift operator.
Because multinuclear transition metal complexes are challenging research subjects of theoretical chemistry, we theoretically investigated electronic structure and
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bonding nature of several dinuclear and trinuclear complexes. For instance, rhenium dinuclear complexes requested us to use multi-reference electronic structure theory. Those rhenium dinuclear complexes have metal-metal bond, bond order of which is much smaller than the formal value.
Light-induced spin-trapping complex is one of interesting materials, recently, because of their potential abilities for molecular devices. We theoretically investigated light-induced spin trapping feature of iron(III) complex. Interestingly, the potential energy surface of the intermediate spin state is rather close to those of the low spin and high spin states, against the general understanding. This new result attracts a lot of interests from the experimental field.
Catalytic reaction by transition metal complexes is very interesting in theoretical chemistry, because such catalyses are useful and complicated in general. Here, iridium-catalyzed direct silylation of benzene was theoretically investigated. Our theoretical study clearly shows that active species is iridium(V) complex and the catalytic reaction takes place through iridium(III) and iridium(V) species. Less
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