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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Quantifying the binding strength of salicylaldoxime-uranyl complexes relative to competing salicylaldoxime-transition metal ion complexes in aqueous solution: a combined experimental and computational study
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Quantifying the binding strength of salicylaldoxime-uranyl complexes relative to competing salicylaldoxime-transition metal ion complexes in aqueous solution: a combined experimental and computational study

机译：相对于竞争的水杨醛肟-过渡金属离子络合物定量水杨醛醛肟-铀酰复合物的结合强度：结合实验和计算研究

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The design of new ligands and investigation of UO22+ complexations are an essential aspect of reducing the cost of extracting uranium from seawater, improving the sorption efficiency for uranium and the selectivity for uranium over competing ions (such as the transition metal cations). The binding strengths of salicylaldoxime-UO22+ complexes were quantified for the first time and compared with the binding strengths of salicylic acid-UO22+ and representative amidoxime-UO22+ complexes. We found that the binding strengths of salicylaldoxime-UO22+ complexes are similar to 2-4 log beta(2) units greater in magnitude than their corresponding salicylic acid-UO22+ and representative amidoxime-UO22+ complexes; moreover, the selectivity of salicylaldoxime towards the UO22+ cation over competing Cu2+ and Fe3+ cations is far greater than those reported for salicylic acid and glutarimidedioxime in the literature. The higher UO22+ selectivity can likely be attributed to the different coordination modes observed for salicylaldoxime-UO22+ and salicylaldoxime-transition metal complexes. Density functional theory calculations indicate that salicylaldoxime can coordinate with UO22+ as a dianion species formed by eta(2) coordination of the aldoximate and monodentate binding of the phenolate group. In contrast, salicylaldoxime coordinates with transition metal cations as a monoanion species via a chelate formed between phenolate and the oxime N; the complexes are stabilized via hydrogen bonding interactions between the oxime OH group and phenolate. By coupling the experimentally determined thermodynamic constants and the results of theoretical computations, we are able to derive a number of ligand design principles to further improve the UO22+ cation affinity, and thus further increase the selectivity of salicylaldoxime derivatives.
机译：新配体的设计和UO22 +络合物的研究是降低从海水中提取铀的成本，提高铀的吸附效率和铀对竞争离子（例如过渡金属阳离子）的选择性的重要方面。首次定量测定了水杨醛肟-UO22 +复合物的结合强度，并与水杨酸-UO22 +和代表性的mid胺肟-UO22 +复合物的结合强度进行了比较。我们发现，水杨醛肟-UO22 +复合物的结合强度类似于2-4 log beta（2）单位，其强度大于其相应的水杨酸-UO22 +和代表性的a胺肟-UO22 +复合物;此外，水杨醛肟对UO22 +阳离子的竞争性优于竞争性的Cu2 +和Fe3 +阳离子，其选择性远高于文献中报道的水杨酸和戊二酰胺肟的选择性。较高的UO22 +选择性可能归因于水杨醛肟-UO22 +和水杨醛肟-过渡金属配合物观察到的不同配位模式。密度泛函理论计算表明，水杨醛肟可与UO22 +协同作用，它是由醛酸酯与酚盐基团的单齿键合eta（2）配位形成的二价阴离子。相反，水杨醛肟通过在酚盐和肟N之间形成的螯合物与过渡金属阳离子配成单阴离子物质。配合物通过肟OH基团和酚盐之间的氢键相互作用而稳定。通过结合实验确定的热力学常数和理论计算结果，我们能够得出许多配体设计原理，以进一步提高UO22 +阳离子亲和力，从而进一步提高水杨醛肟衍生物的选择性。

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