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

被引:8
|
作者
Johnson, Aaron T. [1 ]
Parker, T. Gannon [2 ]
Dickens, Sara M. [3 ]
Pfeiffer, Jana K. [1 ]
Oliver, Allen G. [4 ]
Wall, Donald [3 ]
Wall, Nathalie A. [2 ]
Finck, Martha R. [1 ]
Carney, Kevin P. [1 ]
机构
[1] Idaho Natl Lab, Global Secur & Int Safeguards, Idaho Falls, ID 83401 USA
[2] Washington State Univ, Dept Chem, Pullman, WA 99164 USA
[3] Washington State Univ, Nucl Radiat Ctr, Pullman, WA 99164 USA
[4] Univ Notre Dame, Dept Chem & Biochem, Notre Dame, IN 46556 USA
关键词
QUADRIVALENT ACTINIDES; NUCLEAR FORENSICS; BEHAVIOR;
D O I
10.1021/acs.inorgchem.7b02290
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Production of certified reference materials in support of domestic nuclear forensics programs require volatile precursors for introduction into electromagnetic isotopic separation instruments. beta-Diketone chelates of tetravalent actinides are known for their high volatility, but previously developed synthetic approaches require starting material (NpCI4) 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 beta-diketone ligands of varying degrees of fluorination were reacted with an aqueous solution of Np4+. 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 beta-diketonates by this approach circumvents the necessity of using NpCl4 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 degrees 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 beta-diketonates make them ideal candidates for gaseous introduction into isotopic separation instruments.
引用
收藏
页码:13553 / 13561
页数:9
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