Neptunyl Peroxide Chemistry: Synthesis and Spectroscopic Characterization of a Neptunyl Triperoxide Compound, Ca2[NpO2(O2)3]·9H2O

Sarah Hickam; Debmalya Ray; Jennifer E.S. Szymanowski; Ru Ye Li; Mateusz Dembowski; Philip Smith; Laura Gagliardi; Peter C. Burns

doi:10.1021/acs.inorgchem.9b01712

Neptunyl Peroxide Chemistry: Synthesis and Spectroscopic Characterization of a Neptunyl Triperoxide Compound, Ca₂[NpO₂(O₂)₃]·9H₂O

Sarah Hickam, Debmalya Ray, Jennifer E.S. Szymanowski, Ru Ye Li, Mateusz Dembowski, Philip Smith, Laura Gagliardi, Peter C. Burns

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

Little is known about the crystal chemistry of neptunyl peroxide compounds compared to uranyl peroxide compounds, for which dozens of structures have been described. Uranyl peroxides are formed over a broad range of pH and solution conditions, but neptunyl peroxide chemistry is complicated by the ability of H₂O₂ to act as an oxidizing or reducing agent for Np, depending on the conditions present. The combination of Np(V) in 1 M HCl, H₂O₂, and CaCl₂ under alkaline conditions leads to the immediate crystallization of a neptunyl triperoxide monomer, Ca₂[NpO₂(O₂)₃]·9H₂O, which is the first Np(VI)-based peroxide compound to be characterized in the solid state and is isostructural to Ca₂[UO₂(O₂)₃]·9H₂O. The crystal structure reveals bond distances of 1.842(7) Å that are the longest reported to date for nonbridging Np(VI)-O_yl bonds. Computational studies probe the oxidation state and bond distances of the monomer unit and differences in Raman spectra of the neptunyl and uranyl triperoxide compounds.

Original language	English
Pages (from-to)	12264-12271
Number of pages	8
Journal	Inorganic Chemistry
Volume	58
Issue number	18
DOIs	https://doi.org/10.1021/acs.inorgchem.9b01712
State	Published - Sep 16 2019
Externally published	Yes

Funding

This research was funded by the U.S. Department of Energy, National Nuclear Security Administration, under Award Number DE-NA0003763. The authors thank Dr. Sergey M. Aksenov for his help with the VDP analysis. We thank the Materials Characterization Facility for some of the instrumentation used in this work.

Funders	Funder number
U.S. Department of Energy
National Nuclear Security Administration	DE-NA0003763

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title = "Neptunyl Peroxide Chemistry: Synthesis and Spectroscopic Characterization of a Neptunyl Triperoxide Compound, Ca2[NpO2(O2)3]·9H2O",

abstract = "Little is known about the crystal chemistry of neptunyl peroxide compounds compared to uranyl peroxide compounds, for which dozens of structures have been described. Uranyl peroxides are formed over a broad range of pH and solution conditions, but neptunyl peroxide chemistry is complicated by the ability of H2O2 to act as an oxidizing or reducing agent for Np, depending on the conditions present. The combination of Np(V) in 1 M HCl, H2O2, and CaCl2 under alkaline conditions leads to the immediate crystallization of a neptunyl triperoxide monomer, Ca2[NpO2(O2)3]·9H2O, which is the first Np(VI)-based peroxide compound to be characterized in the solid state and is isostructural to Ca2[UO2(O2)3]·9H2O. The crystal structure reveals bond distances of 1.842(7) {\AA} that are the longest reported to date for nonbridging Np(VI)-Oyl bonds. Computational studies probe the oxidation state and bond distances of the monomer unit and differences in Raman spectra of the neptunyl and uranyl triperoxide compounds.",

author = "Sarah Hickam and Debmalya Ray and Szymanowski, {Jennifer E.S.} and Li, {Ru Ye} and Mateusz Dembowski and Philip Smith and Laura Gagliardi and Burns, {Peter C.}",

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Neptunyl Peroxide Chemistry: Synthesis and Spectroscopic Characterization of a Neptunyl Triperoxide Compound, Ca₂[NpO₂(O₂)₃]·9H₂O

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