Abstract
A macrocyclic trinuclear complex of (1,3,5-trimethylbenzene)ruthenium(II) bridged by 2,3-dioxopyridine was synthesized, and the extraction properties for lithium and sodium picrates were investigated in a dichloromethane/water system at 25°C. The complex was found to have extremely high extractability and selectivity for lithium picrate; the logarithmic values of the extraction constants are 5.86 and 2.63 for Li+ and Na+, respectively. By using this complex as an extractant, nearly quantitative extraction and separation of Li+ from Na+ could be achieved by a single extraction.
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Typical synthetic procedure: A suspension of [(1,3,5-trimethylbenzene)RuCl2]2 (1.75 g, 3.00 mmol), 2,3-dihydroxypyridine (0.667 g, 6.00 mmol), and cesium carbonate (4.89 g, 15.0 mmol) in degassed methanol (120 cm3) was stirred for 1 h under nitrogen atmosphere. After the solvent was evaporated, the product was extracted with degassed dichloromethane. The dichloromethane solution was washed twice with deionized water, and then filtered, evaporated, and dried under reduced pressure, leaving a brown powder (1.43 g, yield 72%). 1H NMR (400 MHz, CDCl3, TMS): δ (ppm) = 2.19 (s, 27H; CH3), 4.75 (s, 9H; C6H3(CH3)3), 5.68 (dd, J = 6.7, 6.7 Hz, 3H; CH, dioxopyridine), 6.10 (d, J = 7.2 Hz, 3H; CH, dioxopyridine), 6.65 (d, J = 6.0 Hz, 3H; CH, dioxopyridine); 13C NMR (100 MHz, CDCl3, TMS): d (ppm) = 18.6 (CH3), 73.7, 100.7 (C6H3(CH3)3), 109.9, 113.9, 132.9, 157.3, 171.0 (dioxopyridine); MS (FAB+): m/z = 992 [M+–H]. Small amounts of water (1.7 wt%) and dichloromethane (4 wt%) were detected by Karl–Fischer titrations and 1H NMR, respectively, indicating that the formation of 3·H2O·0.5CH2Cl2. Elemental analysis data supported this composition (Anal. calcd. for C42H45N3O6Ru3·H2O·0.5CH2Cl2: C, 48.5; H, 4.6; O, 4.0. Found: C, 48.1; H, 4.6; O, 4.0).
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Katsuta, S., Imoto, T., Kudo, Y. et al. Selective Extraction of Lithium with a Macrocyclic Trinuclear Complex of (1,3,5-Trimethylbenzene)ruthenium(II) Bridged by 2,3-Dioxopyridine. ANAL. SCI. 24, 1215–1217 (2008). https://doi.org/10.2116/analsci.24.1215
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DOI: https://doi.org/10.2116/analsci.24.1215