Inorg Chem. 2015 Nov 02;54(21):10323-34. doi: 10.1021/acs.inorgchem.5b01699. Epub 2015 Oct 19.
Inorganic chemistry
Steven P Kelley, Robin D Rogers
PMID: 26479078 DOI: 10.1021/acs.inorgchem.5b01699
An ionic liquid (IL) approach for soft-donor f-element chemistry has been demonstrated by the isolation of several new uranyl dicyanamide complexes through reactions of UO2(NO3)2·6H2O with dicyanamide ([N(CN)2](-))-containing ILs. The [N(CN)2](-) ions are able to rapidly substitute uranium's O-donor ligands, as evidenced by single-crystal X-ray diffraction studies on two anhydrous adducts of UO2(NO3)2 with [N(CN)2](-) ILs as well as by IR and NMR spectroscopic studies on solutions of UO2(NO3)2 in these ILs. By contrast, the slow reaction of UO2(OAc)2·2H2O with a nitrile-functionalized imidazolium dicyanamide IL in solvent and the reaction of UO2(NO3)2·6H2O with NaN(CN)2 at elevated temperature resulted in irreversible hydrolysis. The reaction of UO2SO4 with [N(CN)2](-) ions in an acidified aqueous solution resulted in the crystallization of a [UO2](2+) complex with biuret, a N(CN)2](-) hydrolysis product. [N(CN)2](-) ions in the form of ILs react rapidly with [UO2](2+) at room temperature, allowing ligand substitution with [N(CN)2](-) to out-compete the slower hydrolysis reaction, enabling the isolation of uranyl dicyanamide complexes and challenging assumptions regarding the affinity of uranium for O-donors.
