| Project/Area Number |
15105001
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| Research Category |
Grant-in-Aid for Scientific Research (S)
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| Allocation Type | Single-year Grants |
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| Research Field |
Organic chemistry
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| Research Institution | The University of Tokyo |
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Principal Investigator |
KAWASHIMA Takayuki The University of Tokyo, Graduate School of Science, Professor (80011766)
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| Co-Investigator(Kenkyū-buntansha) |
KANO Naokazu University of Tokyo, Graduate School of Science, Associate Professor (00302810)
KOBAYASHI Junji University of Tokyo, Graduate School of Science, Associate Professor (90334242)
後藤 敬 東京工業大学, 大学院・理工学研究科, 准教授 (70262144)
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| Project Period (FY) |
2003 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥107,120,000 (Direct Cost: ¥82,400,000、Indirect Cost: ¥24,720,000)
Fiscal Year 2007: ¥19,110,000 (Direct Cost: ¥14,700,000、Indirect Cost: ¥4,410,000)
Fiscal Year 2006: ¥17,550,000 (Direct Cost: ¥13,500,000、Indirect Cost: ¥4,050,000)
Fiscal Year 2005: ¥19,110,000 (Direct Cost: ¥14,700,000、Indirect Cost: ¥4,410,000)
Fiscal Year 2004: ¥21,320,000 (Direct Cost: ¥16,400,000、Indirect Cost: ¥4,920,000)
Fiscal Year 2003: ¥30,030,000 (Direct Cost: ¥23,100,000、Indirect Cost: ¥6,930,000)
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| Keywords | Tetracoordinated 1, 2-iodoxetane / Oxidants / Tetradentate ligand / Carbaphosphatranes / Carbasilatrane / Highly coordinated disilanes / Silanolatoziruconium complex / Amino (ylide) carbene / 三方両錐構造 / 結合定数 / ホスホラニルラジカル / アラトラン / クラスター / トリアリールホスフィン / トリアルキルアルミニウム / X線結晶構造解析 / 高周期14族元素化合物 / 7配位化合物 / 1-アクオ-5-カルバシラトラン / 酸性度 / Atoms in Molecules解析 / デンドリマー / シラノール / カルボキシラート / ジシラン / ジチオカルボキシラート / キャビティー / 1-ヒドロ-5-カルバホスファトラン / 互変異性体 / 環状ホスホナイト / 1-メチル-5-カルバホスファトラン / 3配位1,2-ヨードキセタン / ジフルオロヨードキセタン / 1,2-ヨードキセタン 1-オキシド / 酸化・還元 |
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| Research Abstract |
The object of this study is to develop novel ligands, which occupy the specific positions of hypervalent main group compounds on the basis of the steric and electronic stabilization effects, and synthesize the hypervalent compounds with novel frameworks by use of these ligands. Mainly, we have developed several ligands for pentacoordinated main-group-element compounds, such as a planar tridentate ligand which occupies two apical positions and one equatorial position, tetradentate ligands which occupy three equatorial positions and one apical position, a bulky dendrimer-type ligand which occupies the equatorial position, and the dithiocarboxylato ligand which bridges two highly coordinate main-group elements. As a result, we succeeded in applying tetracoordinated 1,2-iodoxetane as a thermally stable oxidant, synthesizing carbaphosphatranes and a carbasilatrane where three oxygen atoms and one arbon atom occupy the equatorial and apical positions, respectively, and synthesizing disilanes with bonds between pentacoordinated silicon atoms and between heptacoordinated silicon atoms.
In addition, we also succeeded in synthesizing their related compounds such as prophosphaalatrane containing phosphorus and aluminum, a cationic silanolatozirconium complex that has olefin polymerization activity, and an amino(ylide)carbene having the highest electron donating ability among the related carbenes known to date. As mentioned above, we achieved the construction of the novel hypervalent compounds bearing a thermodynamically unfavorable configuration by taking advantages of the ligands that we developed by ourselves and elucidation of their structures, bonding modes, and reactivities. We could obtain new knowledge based on new structures that would contribute significantly to the development of a new paradigm in main group chemistry.
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