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  • Title: Coordination of 1,10-phenanthroline and 2,2'-bipyridine to Li+ in different ionic liquids. How innocent are ionic liquids?
    Author: Schmeisser M, Heinemann FW, Illner P, Puchta R, Zahl A, van Eldik R.
    Journal: Inorg Chem; 2011 Jul 18; 50(14):6685-95. PubMed ID: 21667931.
    Abstract:
    On the basis of (7)Li NMR measurements, we have made detailed studies on the influence of the ionic liquids [emim][NTf(2)], [emim][ClO(4)], and [emim][EtSO(4)] on the complexation of Li(+) by the bidentate N-donor ligands 2,2'-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][ClO(4)] and [emim][EtSO(4)], crystal structures confirmed the NMR data, resulting in the complexes [Li(bipy)(2)ClO(4)] and [Li(phen)(2)EtSO(4)], respectively. On the contrary, the ionic liquid [emim][NTf(2)] generated the C(i) symmetric, dinuclear, supramolecular cluster [Li(bipy)(NTf(2))](2), where the individual Li(+) centers were found to be bridged by two [NTf(2)] anions. Density functional theory (DFT)-calculations lead to further information on the effect of stacking on the coordination geometry of the Li(+) centers.
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