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

Korey P Carter; Kurt F Smith; Toni Tratnjek; Gauthier J.-P Deblonde; Liane M Moreau; Julian A Rees; Corwin H Booth; Rebecca J Abergel

doi:10.1021/acs.inorgchem.0c03088

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

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

Korey P Carter, Kurt F Smith, Toni Tratnjek, Gauthier J.-P Deblonde, Liane M Moreau, Julian A Rees, Corwin H Booth and Rebecca J Abergel

Inorganic chemistry, Vol.60(2), pp.973-981

01/18/2021

DOI: 10.1021/acs.inorgchem.0c03088

PMID: 33356197

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https://www.osti.gov/biblio/1777965View

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Abstract

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 UIV, 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 UIV to a lesser extent, as evidenced by the mix of UIV and UVI complexes observed via XAS. CV and SEC measurements confirmed that the UIV complex formed with 3,4,3-LI(1,2-HOPO) is redox inert in acidic media, and UVI ions can be reduced, likely proceeding via a two-electron reduction process.

Details

Title: Subtitle: Controlling the Reduction of Chelated Uranyl to Stable Tetravalent Uranium Coordination Complexes in Aqueous Solution
Creators: Korey P Carter - Chemical Sciences Division
Kurt F Smith - Chemical Sciences Division
Toni Tratnjek - Chemical Sciences Division
Gauthier J.-P Deblonde - Glenn T. Seaborg Institute, Physical & Life Sciences
Liane M Moreau - Chemical Sciences Division
Julian A Rees - Chemical Sciences Division
Corwin H Booth - Chemical Sciences Division
Rebecca J Abergel - University of California
Resource Type: Journal article
Publication Details: Inorganic chemistry, Vol.60(2), pp.973-981
DOI: 10.1021/acs.inorgchem.0c03088
PMID: 33356197
NLM abbreviation: Inorg Chem
ISSN: 0020-1669
eISSN: 1520-510X
Publisher: American Chemical Society
Grant note: DOI: 10.13039/100006151, name: Basic Energy Sciences, award: DE-AC02-05CH1123
Language: English
Date published: 01/18/2021
Academic Unit: Chemistry
Record Identifier: 9984216708302771

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