Half-sandwich Iridium Complexes Bearing a Diprotic Glyoxime Ligand: Structural Diversity Induced by Reversible Deprotonation.
Half-sandwich Iridium Complexes Bearing a Diprotic Glyoxime Ligand: Structural Diversity Induced by Reversible Deprotonation.
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DOI：
10.1002/asia.201901276
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发表时间：
2019-10
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影响因子：
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通讯作者：
Taishin Takamura;T. Harada;T. Furuta;T. Ikariya;S. Kuwata
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文献类型：
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作者：
Taishin Takamura;T. Harada;T. Furuta;T. Ikariya;S. Kuwata
研究了含邻位二肟配体的半夹心铱配合物的合成和脱质子反应。[{Cp*IrCl（μ-Cl）}2]（Cp* = eta 5-C5 Me 5）与丁二酮肟（LH 2）以1：1的Ir：LH 2比例处理得到阳离子二肟铱配合物[Cp*IrCl（LH 2）]Cl（1）。氯代配合物1与碳酸钾发生逐步可逆的脱质子反应，依次得到肟-肟配合物[Cp*IrCl（LH）]（2）和阴离子二肟（2-）配合物K[Cp*IrCl（L）]（3）。同时，硫酸根配合物[Cp*Ir（SO 4）（LH 2）]（4）的二次去质子化导致肟基桥联双核配合物[{Cp*Ir（mu-L）}2]（5）的形成。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）、六边形开放通道（3）和具有多个分子间氢键和静电相互作用的四聚体菱形（4）。
Synthesis and deprotonation reactions of half-sandwich iridium complexes bearing a vicinal dioxime ligand were studied. Treatment of [{Cp*IrCl(mu-Cl)}2] (Cp* = eta5-C5Me5) with dimethylglyoxime (LH2 ) in an Ir:LH2 ratio of 1:1 afforded the cationic dioxime iridium complex [Cp*IrCl(LH2)]Cl ( 1 ). The chlorido complex 1 undergoes stepwise and reversible deprotonation with potassium carbonate to give the oxime-oximato complex [Cp*IrCl(LH)] ( 2 ) and the anionic dioximato(2-) complex K[Cp*IrCl(L)] ( 3 ) sequentially. Meanwhile, twofold deprotonation of the sulfato complex [Cp*Ir(SO4)(LH2)] ( 4 ) resulted in the formation of the oximato-bridged dinuclear complex [{Cp*Ir(mu-L)}2] ( 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.