| Project/Area Number |
15K05460
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Chuo University |
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Principal Investigator |
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| Co-Investigator(Kenkyū-buntansha) |
小玉 晋太朗 中央大学, 理工学部, 助教 (30612189)
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| Co-Investigator(Renkei-kenkyūsha) |
TAKANO Keiko お茶の水女子大学, 大学院人間文化創成科学研究科, 教授 (00143701)
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| Project Period (FY) |
2015-04-01 – 2018-03-31
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| Project Status |
Completed (Fiscal Year 2017)
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| Budget Amount *help |
¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2016: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
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| Keywords | カリックスアレーン / イリジウム / ロジウム / CH結合活性化 / Cp*配位子 / ハプテシティ変化 / πアリル錯体 / カルベン錯体 / N-ヘテロサイクリックカルベン / C-H結合活性化 / ピラーアレーン / ハプティシティ変化 / 配位子置換 / イソシアニド |
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| Outline of Final Research Achievements |
The first examples of (kappa)3-O,C,O tridentate calix[4]arene transition metal complexes [Cp*Ir{(C6H2tBu)4(CH)(CH2)3(O)(OH)3}] (M = Ir, Rh) that are stable both in the solid state and in solution were synthesized. The reaction of the Ir complex with 2 equiv of xylyl isocyanide afforded the ((eta)1-Cp*)Ir(CNXy)2 complex in which the Cp* ligand is slipped from an (eta)5- to an (eta)1-fashion, although ring slippage of (eta)5-Cp* ligand is by far uncommon compared with that of Cp. The reaction of the ((eta)1-Cp*)Ir complex with additional 1 equiv of isocyanide resulted in the liberation of the Cp* ligand as Cp*H, which is confirmed by 1H NMR. This study provides the first observation of stepwise dissociation of Cp* ligand from group 4-10 transition metals via (eta)1-coordination. This unique phenomenon seems to be facilitated by flexible coordination of an OH group in the C-metallated calix[4]arene ligand.
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