Controlling the Reduction of Chelated Uranyl to Stable Tetravalent Uranium Coordination Complexes in Aqueous Solution,Inorganic Chemistry

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Controlling the Reduction of Chelated Uranyl to Stable Tetravalent Uranium Coordination Complexes in Aqueous Solution
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-12-27 , DOI: 10.1021/acs.inorgchem.0c03088
Korey P. Carter ₁ , Kurt F. Smith ₁ , Toni Tratnjek ₁ , Gauthier J.-P. Deblonde _{1,

2} , Liane M. Moreau ₁ , Julian A. Rees ₁ , Corwin H. Booth ₁ , Rebecca J. Abergel _{1,

3}

Affiliation

The solution-state interactions between octadentate hydroxypyridinone (HOPO) and catecholamide (CAM) chelating ligands and uranium were investigated and characterized by UV–visible spectrophotometry and X-ray absorption spectroscopy (XAS), as well as electrochemically via spectroelectrochemistry (SEC) and cyclic voltammetry (CV) measurements. Depending on the selected chelator, we demonstrate the controlled ability to bind and stabilize U^IV, generating with 3,4,3-LI(1,2-HOPO), a tetravalent uranium complex that is practically inert toward oxidation or hydrolysis in acidic, aqueous solution. At physiological pH values, we are also able to bind and stabilize U^IV to a lesser extent, as evidenced by the mix of U^IV and U^VI complexes observed via XAS. CV and SEC measurements confirmed that the U^IV complex formed with 3,4,3-LI(1,2-HOPO) is redox inert in acidic media, and U^VI ions can be reduced, likely proceeding via a two-electron reduction process.

中文翻译：

控制水溶液中螯合的铀基还原为稳定的四价铀配位络合物

研究了八齿羟基吡啶酮（HOPO）和儿茶酚酰胺（CAM）螯合配体与铀之间的溶液状态相互作用，并通过紫外可见分光光度法和X射线吸收光谱法（XAS）进行了表征，并通过光谱电化学法（SEC）和环状电化学方法进行了表征。伏安法（CV）测量。根据所选的螯合剂，我们证明了结合并稳定U ^IV的可控能力，它与3,4,3-LI（1,2-HOPO）生成的四价铀络合物实际上对酸性下的氧化或水解呈惰性，水溶液。在生理pH值下，我们也能够在较小程度上结合和稳定U ^IV，如U ^IV和U ^VI的混合所证明的那样通过XAS观察到的复合物。CV和SEC测量证实，由3,4,3-LI（1,2-HOPO）形成的U ^IV络合物在酸性介质中是氧化还原惰性的，并且U ^VI离子可以被还原，可能通过两电子还原过程进行。

更新日期：2021-01-18

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