Synthesis and Crystal Structures of Volatile Neptunium(IV) β-Diketonates

Abstract

Production of certified reference materials in support of domestic nuclear forensics programs require volatile precursors for introduction into electromagnetic isotopic separation instruments. β-Diketone chelates of tetravalent actinides are known for their high volatility, but previously developed synthetic approaches require starting material (NpCl) that is prohibitively difficult and hazardous to prepare. An alternative strategy was developed here that uses controlled potential electrolysis to reduce neptunium to the tetravalent state in submolar concentrations of hydrochloric acid. Four different β-diketone ligands of varying degrees of fluorination were reacted with an aqueous solution of Np. Products of this reaction were characterized via X-ray diffraction and infrared spectroscopy, and were found to be neutral 8-coordinate complexes that adopt square antiprismatic crystal geometry. Synthesis of Np β-diketonates by this approach circumvents the necessity of using NpCl in tetravalent Np coordination compound synthesis. The volatility of the complexes was assessed using thermogravimetric analysis, where the temperature of sublimation was determined to be in the range of 180° to 205 °C. The extent of fluorination did not appreciably alter the sublimation temperature of the complex. Thermal decomposition of these compounds was not observed during sublimation. High volatility and thermal stability of Np β-diketonates make them ideal candidates for gaseous introduction into isotopic separation instruments.

Exploring the Oxidation States of Neptunium with Schiff Base Coordination Complexes

“…The O(1)–Np–O(2) and N(1)–Np–N(2) intraligand angles are 85.37(7) and 61.38(7)°, respectively, which compare well with the 84.9(1)–87.40(4)° and 61.6(1)–60.43(4)° ranges of other M IV L 2 complexes. Compared to other eight-coordinate Np IV complexes, the Np–O bonds are significantly shorter than those found in Np­(H 2 L) 2 ·Cl 2 (H 3 L = glutaroimide-dioxime) reported at 2.355(2) and 2.350(2), and in β-diketonate Np­(FOD) 4 (FOD = 6,6,7,­7,8,8,8-hepta­fluoro-2,2-di­methyl-3,5-octane­dione) of 2.290(7)–2.347(6) Å …”

Crystal structure of a trigonal polymorph of aquadioxidobis(pentane-2,4-dionato-κ2 O,O′)uranium(VI)

“…Hexavalent actinide complexes with -diketonates are possibilities for either of these methods. They are neutrally charged, and with appropriate substituents on the -diketonate may be volatile (Johnson et al, 2017).…”