Journal article
Bonding and reactivity of isostructural uranyl and neptunyl peroxide phases
Communications chemistry, Vol.8(1), 385
2025
DOI: 10.1038/s42004-025-01733-6
PMCID: PMC12669678
PMID: 41275035
Abstract
Understanding the reactivity of actinide peroxides is critical for predicting the behavior of spent nuclear fuel in radiolytic environments. Herein, we report the synthesis and characterization of a lithium neptunyl(VI) hydroxo peroxo compound (LiNp), which is isostructural to the uranyl analogue (LiU). Single-crystal X-ray diffraction reveals that LiNp contains both [NpO2(O2)3]4- and [NpO2(OH)4]2- units stabilized by Li+ and hydrogen bonding and Raman spectroscopy shows systematic redshifts in neptunyl vibrational modes relative to uranyl. DFT calculations highlight the importance of secondary coordination in reproducing vibrational and structural features, but challenges remain with correctly modeling strong sigma donors. Solid-state EPR spectroscopy and DFT confirm superoxide stabilization within LiU and calculations suggest favorability of the analogous radical species in LiNp. Solution state EPR spectroscopy with the radical spin trap 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide (BMPO) reveal evidence of superoxide in the LiU and LiNp phases and suggests stabilization of superoxide within actinyl triperoxide complexes, forming [AnO2(O2)2(O)2•]3-.
Details
- Title: Subtitle
- Bonding and reactivity of isostructural uranyl and neptunyl peroxide phases
- Creators
- Harindu Rajapaksha - University of IowaGrant C Benthin - University of IowaEmma L Markun - University of IowaCameron J Flester - University of IowaSara E Mason - University of IowaTori Z Forbes - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Communications chemistry, Vol.8(1), 385
- DOI
- 10.1038/s42004-025-01733-6
- PMID
- 41275035
- PMCID
- PMC12669678
- NLM abbreviation
- Commun Chem
- ISSN
- 2399-3669
- eISSN
- 2399-3669
- Publisher
- Springer Nature
- Grant note
- DE-SC0023995 / U.S. Department of Energy (DOE)
- Language
- English
- Electronic publication date
- 11/22/2025
- Date published
- 2025
- Academic Unit
- Civil and Environmental Engineering; Core Research Facilities; Chemistry
- Record Identifier
- 9985035036902771
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