Properties of Organometallic Complexes Derived from CH Bond Activation of Calixarenes

2017 Fiscal Year Final Research Report

• Project/Area Number: 15K05460
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Chuo University
• Principal Investigator: Ishii Youichi 中央大学, 理工学部, 教授 (40193263)
• Co-Investigator(Kenkyū-buntansha): 小玉 晋太朗 中央大学, 理工学部, 助教 (30612189)
• 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)
• Project Period (FY): 2015-04-01 – 2018-03-31
• 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

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.

Free Research Field

有機金属化学