| Project/Area Number |
22655029
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| Research Category |
Grant-in-Aid for Challenging Exploratory Research
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Kyushu University |
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Principal Investigator |
NAGASHIMA Hideo 九州大学, 先導物質化学研究所, 教授 (50159076)
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| Project Period (FY) |
2010 – 2011
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| Project Status |
Completed (Fiscal Year 2011)
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| Budget Amount *help |
¥3,460,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥360,000)
Fiscal Year 2011: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2010: ¥1,900,000 (Direct Cost: ¥1,900,000)
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| Keywords | 元素戦略 / 鉄 / 分子触媒 / 酸化還元 / 共役付加 / エノレート / 鉄錯体 / 鉄触媒 / カップリング / 1,2-付加 / エノレート生成 |
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| Research Abstract |
Three types of coordinatively unsaturated iron species were designed by appropriate choice of auxialiry ligands, and their reactivity towards alkenes and related unsaturated compounds was investigated. Triazacyclononane(TACN) derivatives were a good ligand for Fe(II) complexes. Coordinatively unsaturated 16e-(TACN) FeX2 species behaved as a catalyst for atom transfer radical polymerization. Two concepts for generation of 16e-Fe(II) species were proposed ; one was based on favorable equiliblim between a halogen-bridged dimer and a catalytically active monomer controlled by steric bulkiness of nitrogen substituents of TACN, whereas another was stabilization of active monomeric species by weakly coordinating ligands. Treatment of a 14e-organoiron complex bearing two mesityl groups and a tetraethylenediamine ligand with electron deficient alkenes resulted in coupling reaction of the mesityl ligands as well as conjugate addition of a mesityl group toα,β-unsaturated ketones. Disilametallacylic 16e-Fe(II) species was generated from a nitrogen-bridged dimer precursor reacted with alkenes to form cyclic organosilicon compounds.
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