Spontaneous Chelation-Driven Reduction of the Neptunyl Cation in Aqueous Solution

Carter, Korey P.; Smith, Kurt F.; Tratnjek, Toni; Shield, Katherine M.; Moreau, Liane M.; Rees, Julian A.; Booth, Corwin H.; Abergel, Rebecca J.

doi:10.1002/chem.201905695

Title: Spontaneous Chelation-Driven Reduction of the Neptunyl Cation in Aqueous Solution

Journal Article · Wed Jan 08 00:00:00 UTC 2020 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.201905695 · OSTI ID:1631631

^[1]; Smith, Kurt F. ^[1]; Tratnjek, Toni ^[1];

^[2]; Moreau, Liane M. ^[1];

^[1]; Booth, Corwin H. ^[1];

^[2]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

Octadentate hydroxypyridinone (HOPO) and catecholamide (CAM) siderophore analogues are known to be efficacious chelators of the actinide cations, and these ligands are also capable of facilitating both activation and reduction of actinyl species. Utilizing X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies, as well as cyclic voltammetry measurements, herein, we elucidate chelation-based mechanisms for driving reactivity and initiating redox processes in a family of neptunyl-HOPO and CAM complexes. Based on the selected chelator, the ability to control the oxidation state of neptunium and the speed of reduction and concurrent oxo group activation was demonstrated. Most notably, reduction kinetics for the Np^V O₂ +/ /Np^IV redox couple upon chelation by the ligands 3,4,3-LI(1,2-HOPO) and 3,4,3-LI(CAM)₂ (1,2-HOPO)₂ was observed to be faster than ever reported, and in fact quicker than we could measure using either X-ray absorption spectroscopy or electrochemical techniques.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1631631

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 11 Vol. 26; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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