Coordination of 1,10-Phenanthroline and 2,2鈥?Bipyridine to Li+ in Different Ionic Liquids. How Innocent Are Ionic Liquids?

详细信息    查看全文

• 作者：Matthias Schmeisser ; Frank W. Heinemann ; Peter Illner ; Ralph Puchta ; Achim Zahl ; Rudi van Eldik
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：July 18, 2011
• 年：2011
• 卷：50
• 期：14
• 页码：6685-6695
• 全文大小：1165K
• 年卷期：v.50,no.14(July 18, 2011)
• ISSN：1520-510X

文摘

On the basis of ⁷Li NMR measurements, we have made detailed studies on the influence of the ionic liquids [emim][NTf₂], [emim][ClO₄], and [emim][EtSO₄] on the complexation of Li⁺ by the bidentate N-donor ligands 2,2鈥?bipyridine (bipy) and 1,10-phenanthroline (phen). For each of the employed ionic liquids the NMR data implicate the formation of [Li(bipy)₂]⁺ and [Li(phen)₂]⁺, respectively. X-ray diffraction studies were performed to determine the coordination pattern in the solid state. In the case of [emim][ClO₄] and [emim][EtSO₄], crystal structures confirmed the NMR data, resulting in the complexes [Li(bipy)₂ClO₄] and [Li(phen)₂EtSO₄], respectively. On the contrary, the ionic liquid [emim][NTf₂] generated the C_i symmetric, dinuclear, supramolecular cluster [Li(bipy)(NTf₂)]₂, where the individual Li⁺ centers were found to be bridged by two [NTf₂] anions. Density functional theory (DFT)-calculations lead to further information on the effect of stacking on the coordination geometry of the Li⁺ centers.