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Issue 86, 2020
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Trimeric uranyl(vi)–citrate forms Na+, Ca2+, and La3+ sandwich complexes in aqueous solution

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Abstract

M. Basile, et al., Chem. Commun., 2015, 51, 5306–5309, showed that a sodium ion is sandwiched by uranyl(VI) oxygen atoms of two 3 : 3 uranyl(VI)–citrate complex molecules in single-crystals. By means of NMR spectroscopy supported by DFT calculations we provide unambiguous evidence for this complex to persist in aqueous solution above a critical concentration of 3 mM uranyl citrate. Unprecedented Ca2+ and La3+ coordination by a bis-(η3-uranyl(VI)-oxo) motif advances the understanding of uranium's aqueous chemistry. As determined from 17O NMR, Ca2+ and more distinctly La3+ cause strong O[double bond, length as m-dash]U[double bond, length as m-dash]O polarization, which opens up new ways for uranyl(VI)-oxygen activation and functionalization.

Graphical abstract: Trimeric uranyl(vi)–citrate forms Na+, Ca2+, and La3+ sandwich complexes in aqueous solution

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Article information


Submitted
11 Aug 2020
Accepted
16 Sep 2020
First published
28 Sep 2020

Chem. Commun., 2020,56, 13133-13136
Article type
Communication

Trimeric uranyl(VI)–citrate forms Na+, Ca2+, and La3+ sandwich complexes in aqueous solution

J. Kretzschmar, S. Tsushima, B. Drobot, R. Steudtner, K. Schmeide and T. Stumpf, Chem. Commun., 2020, 56, 13133
DOI: 10.1039/D0CC05460G

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