Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1 E4-1 O-okayama, Meguro-ku, Tokyo, 152-8552, Japan.
Chem Asian J. 2020 Jan 2;15(1):72-78. doi: 10.1002/asia.201901276. Epub 2019 Oct 22.
Synthesis and deprotonation reactions of half-sandwich iridium complexes bearing a vicinal dioxime ligand were studied. Treatment of [{CpIrCl(μ-Cl)} ] (Cp=η -C Me ) with dimethylglyoxime (LH ) at an Ir:LH ratio of 1:1 afforded the cationic dioxime iridium complex [CpIrCl(LH )]Cl (1). The chlorido complex 1 undergoes stepwise and reversible deprotonation with potassium carbonate to give the oxime-oximato complex [CpIrCl(LH)] (2) and the anionic dioximato(2-) complex K[CpIrCl(L)] (3) sequentially. Meanwhile, twofold deprotonation of the sulfato complex [CpIr(SO )(LH )] (4) resulted in the formation of the oximato-bridged dinuclear complex [{Cp*Ir(μ-L)} ] (5). X-ray analyses disclosed their supramolecular structures with one-dimensional infinite chain (1 and 2), hexagonal open channels (3), and a tetrameric rhomboid (4) featuring multiple intermolecular hydrogen bonds and electrostatic interactions.
研究了含有顺式二肟配体的半夹心铱配合物的合成和去质子化反应。在 Ir:LH 为 1:1 的条件下，用二甲基乙二肟（LH）处理[{CpIrCl(μ-Cl)} ]（Cp=η-C Me ），得到阳离子二肟铱配合物[CpIrCl(LH )]Cl（1）。氯配合物 1 与碳酸钾分步可逆地去质子化，依次得到肟-肟酸盐配合物[CpIrCl(LH)]（2）和阴离子二肟酸盐（2-）配合物 K[CpIrCl(L)]（3）。同时，硫酸根配合物[CpIr(SO )(LH )]（4）的两次去质子化导致形成肟桥联双核配合物[{Cp*Ir(μ-L)} ]（5）。X 射线分析揭示了它们的超分子结构，具有一维无限链（1 和 2）、六方开放通道（3）和具有多个分子间氢键和静电相互作用的四边形菱形（4）。
