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

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)-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.