Tetrahydrosalen Uranyl(VI) Complexes: Crystal Structures and Solution Binding Study

Tetrahydrosalen Uranyl(VI) Complexes: Crystal Structures and Solution Binding Study A pair of uranyl complexes incorporating tetrahydrosalen and N,N‐dimethyltetrahydrosalen ligands are synthesized and studied. These new ligands, with saturated secondary and tertiary amines, exhibit higher chemostability than the prototype Schiff base (salen) structure, especially under acidic conditions. As shown by X‐ray diffraction crystallography, the coordination geometry of uranium in these new complexes is a distorted pentagonal bipyramid. Interestingly, UO2([H4]‐salen), comprising the tetrahydrosalen ligand, forms a dimeric structure in the crystals, with two subunits held together by sharing one of the two phenoxy oxygen atoms from each subunit, whereas UO2([H2Me2]‐salen) with the N,N‐dimethyltetrahydrosalen ligand is in the monomer state, with a solvent molecule coordinated to uranium to complete the penta‐coordination configuration. Moreover, as revealed by UV/Vis spectroscopy using the colorimetry method, these hydrogenated salen ligands exhibit comparable, or even higher, binding affinities toward uranyl than the prototype Schiff base salen ligand in weakly basic solution. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png European Journal of Inorganic Chemistry Wiley

Tetrahydrosalen Uranyl(VI) Complexes: Crystal Structures and Solution Binding Study

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Publisher
Wiley Subscription Services, Inc., A Wiley Company
Copyright
© 2018 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
ISSN
1434-1948
eISSN
1099-0682
D.O.I.
10.1002/ejic.201701401
Publisher site
See Article on Publisher Site

Abstract

A pair of uranyl complexes incorporating tetrahydrosalen and N,N‐dimethyltetrahydrosalen ligands are synthesized and studied. These new ligands, with saturated secondary and tertiary amines, exhibit higher chemostability than the prototype Schiff base (salen) structure, especially under acidic conditions. As shown by X‐ray diffraction crystallography, the coordination geometry of uranium in these new complexes is a distorted pentagonal bipyramid. Interestingly, UO2([H4]‐salen), comprising the tetrahydrosalen ligand, forms a dimeric structure in the crystals, with two subunits held together by sharing one of the two phenoxy oxygen atoms from each subunit, whereas UO2([H2Me2]‐salen) with the N,N‐dimethyltetrahydrosalen ligand is in the monomer state, with a solvent molecule coordinated to uranium to complete the penta‐coordination configuration. Moreover, as revealed by UV/Vis spectroscopy using the colorimetry method, these hydrogenated salen ligands exhibit comparable, or even higher, binding affinities toward uranyl than the prototype Schiff base salen ligand in weakly basic solution.

Journal

European Journal of Inorganic ChemistryWiley

Published: Jan 14, 2018

Keywords: ; ; ; ;

References

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