Influencing Bonding Interactions of the Neptunyl (V, VI) Cations with Electron-Donating and -Withdrawing Groups

Logan J Augustine; Joseph M Kasper; Tori Z Forbes; Sara E Mason; Enrique R Batista; Ping Yang

doi:10.1021/acs.inorgchem.2c04538

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Influencing Bonding Interactions of the Neptunyl (V, VI) Cations with Electron-Donating and -Withdrawing Groups

Journal article

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Influencing Bonding Interactions of the Neptunyl (V, VI) Cations with Electron-Donating and -Withdrawing Groups

Logan J Augustine, Joseph M Kasper, Tori Z Forbes, Sara E Mason, Enrique R Batista and Ping Yang

Inorganic chemistry, Vol.62(15), pp.6055-6064

04/17/2023

DOI: 10.1021/acs.inorgchem.2c04538

PMID: 37000037

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https://www.osti.gov/servlets/purl/1969244View

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Abstract

Neptunium makes up the largest percentage of minor actinides found in spent nuclear fuel, yet separations of this element have proven difficult due to its rich redox chemistry. Developing new reprocessing techniques should rely on understanding how to control the Np oxidation state and its interactions with different ligands. Designing new ligands for separations requires understanding how to properly tune a system toward a desired trait through functionalization. Emerging technologies for minor actinide separations focus on ligands containing carboxylate or pyridine functional groups, which are desirable due to their high degree of functionalization. Here, we use DFT calculations to study the interactions of carboxylate and polypyridine ligands with the neptunyl cation [Np(V/VI)O ] . A systematic study is performed by varying the electronic properties of the carboxylate and polypyridine ligands through the inclusion of different electron-withdrawing and electron-donating groups. We focus on how these groups can affect geometric properties, electronic structure, and bonding characterization as a function of the metal oxidation state and ligand character and discuss how these factors can play a role in neptunium ligand design principles.

Details

Title: Subtitle: Influencing Bonding Interactions of the Neptunyl (V, VI) Cations with Electron-Donating and -Withdrawing Groups
Creators: Logan J Augustine - Department of Chemistry, University of Iowa, Iowa City, Iowa 52245, United States
Joseph M Kasper - Los Alamos National Laboratory
Tori Z Forbes - University of Iowa
Sara E Mason - University of Iowa
Enrique R Batista - Los Alamos National Laboratory
Ping Yang - Los Alamos National Laboratory
Resource Type: Journal article
Publication Details: Inorganic chemistry, Vol.62(15), pp.6055-6064
DOI: 10.1021/acs.inorgchem.2c04538
PMID: 37000037
NLM abbreviation: Inorg Chem
ISSN: 0020-1669
eISSN: 1520-510X
Grant note: DOI: 10.13039/100000015, name: U.S. Department of Energy, award: DE-SC0014664, KC0302020
Language: English
Electronic publication date: 03/31/2023
Date published: 04/17/2023
Academic Unit: Civil and Environmental Engineering; Core Research Facilities; Chemistry
Record Identifier: 9984381133702771

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