| Project/Area Number |
14078221
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Kyoto University |
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Principal Investigator |
SAKAKI Shigeyoshit Kyoto University, Department of Molecular Engineering, Professor, 工学研究科, 教授 (20094013)
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| Project Period (FY) |
2002 – 2005
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥24,000,000 (Direct Cost: ¥24,000,000)
Fiscal Year 2005: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 2004: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 2003: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 2002: ¥6,000,000 (Direct Cost: ¥6,000,000)
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| Keywords | Theoretical study / Transition-metal complexes / Bonding nature / Reaction mechanism / Reactivity control / Geometry / Reactivity / Electronic structure / 電子状態理論 / 動的遷移金属錯体 / 触媒作用 / 理論研究 / 物性制御 / 電子状態制御 / 錯体触媒反応 / 遷移状 / 動的挙動 / シリル錯体 / 前周期遷移金属錯体 / 後周期遷移金属錯体 / 遷移金属元素 / ヘテロ元素 / 二核金属錯体 / 理論的研究 / 多元素複合環状化合物 / agostic相互作用 / 2中心3電子結合 / シリレン架橋錯体 / トランスメタル化反応 / 二酸化炭素固定化反応 / パラジウム錯体 / ロジウム錯体 / ルテニウム錯体 / メタセシス |
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| Research Abstract |
Geometries and reaction behavior of dymamic complexes including transition metal elements were theoretically investigated to clarify how electronic structure detennines geometry and reactivity with DFT and post-Hariree-Fock methods such as MP2 to MP4(SDQ) and CCSD(T) methods. One of the important results is the bonding nature and binding energy of the transition metal complexes with large p-conjugate systems such as C60, corannulene, and sumanene. The DFT method underestimates the binding energy in Pt(0), Ir(I), and similar complexes and the best way now is to employ the ONIOM method, in which the MP4(SDQ) is used for important moiety and the MM method with UFF force field is used for whole molecule. We successfully presented reasonable binding energies of these complexes and proposed that various complexes can be synthesized for corannulene and sumanene. Also, important result is presented on the transition-metal catalyzed synthetic reaction such as Ir-catalyzed direct borylation of benzene with diborane. This reaction takes place through the oxidative addition to Ir(III)-tris bowl active species followed by reductive elimination of bowlbenzene. The important point is that the active species is Ir(III) species and the catalytic cycle involves the Ir(V) intermediate. Also, we theoretically investigated H-H bond activation by S-bridged dinuclear Ru-W complex, which is an interesting model of hydrogenase. The activation reaction takes place through heterolytic sigma bond activation, which is different from the usual oxidative addition reaction. This result clearly shows that the S-bridge Ru-W dinuclear complex is a good functional model ofhydrogenase.
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