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Title: Neptunyl Peroxide Chemistry: Synthesis and Spectroscopic Characterization of a Neptunyl Triperoxide Compound, Ca 2[NpO 2(O 2) 3]·9H 2O

Abstract

Not much 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 H 2O 2 to act as an oxidizing or reducing agent for Np, depending on the conditions present. The combination of Np(V) in 1 M HCl, H 2O 2, and CaCl 2 under alkaline conditions leads to the immediate crystallization of a neptunyl triperoxide monomer, Ca 2[NpO 2(O 2) 3]·9H 2O, which is the first Np(VI)-based peroxide compound to be characterized in the solid state and is isostructural to Ca 2[UO 2(O 2) 3]·9H 2O. 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.

Authors:
 [1]; ORCiD logo [2];  [1];  [2]; ORCiD logo [3];  [1]; ORCiD logo [1]; ORCiD logo [4]
  1. Univ. of Notre Dame, Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute
  3. Univ. of Notre Dame, Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry
  4. Univ. of Notre Dame, Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences; Univ. of Notre Dame, Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Univ. of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1561852
Grant/Contract Number:  
NA0003763
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 58; Journal Issue: 18; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Hickam, Sarah, Ray, Debmalya, Szymanowski, Jennifer E. S., Li, Ru-Ye, Dembowski, Mateusz, Smith, Philip, Gagliardi, Laura, and Burns, Peter C. Neptunyl Peroxide Chemistry: Synthesis and Spectroscopic Characterization of a Neptunyl Triperoxide Compound, Ca2[NpO2(O2)3]·9H2O. United States: N. p., 2019. Web. doi:10.1021/acs.inorgchem.9b01712.
Hickam, Sarah, Ray, Debmalya, Szymanowski, Jennifer E. S., Li, Ru-Ye, Dembowski, Mateusz, Smith, Philip, Gagliardi, Laura, & Burns, Peter C. Neptunyl Peroxide Chemistry: Synthesis and Spectroscopic Characterization of a Neptunyl Triperoxide Compound, Ca2[NpO2(O2)3]·9H2O. United States. doi:10.1021/acs.inorgchem.9b01712.
Hickam, Sarah, Ray, Debmalya, Szymanowski, Jennifer E. S., Li, Ru-Ye, Dembowski, Mateusz, Smith, Philip, Gagliardi, Laura, and Burns, Peter C. Mon . "Neptunyl Peroxide Chemistry: Synthesis and Spectroscopic Characterization of a Neptunyl Triperoxide Compound, Ca2[NpO2(O2)3]·9H2O". United States. doi:10.1021/acs.inorgchem.9b01712.
@article{osti_1561852,
title = {Neptunyl Peroxide Chemistry: Synthesis and Spectroscopic Characterization of a Neptunyl Triperoxide Compound, Ca2[NpO2(O2)3]·9H2O},
author = {Hickam, Sarah and Ray, Debmalya and Szymanowski, Jennifer E. S. and Li, Ru-Ye and Dembowski, Mateusz and Smith, Philip and Gagliardi, Laura and Burns, Peter C.},
abstractNote = {Not much 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)-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.},
doi = {10.1021/acs.inorgchem.9b01712},
journal = {Inorganic Chemistry},
number = 18,
volume = 58,
place = {United States},
year = {2019},
month = {8}
}

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This content will become publicly available on August 26, 2020
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