Crawford Margaret-Jane, Mayer Peter
Department of Chemistry and Biochemistry, Ludwig-Maximilian University (LMU), Butenandtstrasse 5-13 (Haus D), D-81377 Munich, Germany.
Inorg Chem. 2005 Nov 14;44(23):8481-5. doi: 10.1021/ic050409v.
The synthesis and characterization of the ternary U-O-N compound NO(+)UO2(NO3)3- (1) using IR and low-temperature and room-temperature Raman spectroscopy as well as 14N and 15N NMR spectroscopy are reported. In addition, solution Raman spectra of compound 1 recorded in various solvents are reported. The structure of compound 1 was determined using single-crystal X-ray diffraction techniques: monoclinic, C2/c, a = 13.3992(4) angstroms, b = 9.9781(4) angstroms, c = 7.6455(2) angstroms, beta = 115.452(2) degrees, V = 922.98(5) angstroms3, Z = 4. Compound 1 is highly moisture-sensitive and must be handled under an inert atmosphere. It reacts with water with the liberation of NO2. For the first time, this important precursor for the synthesis of anhydrous uranyl nitrate could be unambiguously identified and has been shown to be an ionic nitrosonium salt and not an adduct between uranyl nitrate and dinitrogen tetroxide, UO2(NO3)2.N2O4, as is incorrectly and predominantly cited in the literature.
报道了采用红外光谱、低温及室温拉曼光谱以及¹⁴N和¹⁵N核磁共振光谱对三元U - O - N化合物NO⁺UO₂(NO₃)₃⁻（1）进行的合成与表征。此外，还报道了化合物1在各种溶剂中的溶液拉曼光谱。使用单晶X射线衍射技术确定了化合物1的结构：单斜晶系，C2/c，a = 13.3992(4)埃，b = 9.9781(4)埃，c = 7.6455(2)埃，β = 115.452(2)°，V = 922.98(5)埃³，Z = 4。化合物1对水分高度敏感，必须在惰性气氛下处理。它与水反应会释放出NO₂。首次明确鉴定出这种用于合成无水硝酸铀酰的重要前体，并且已证明它是一种离子型亚硝鎓盐，而不是文献中错误且普遍引用的硝酸铀酰与四氧化二氮的加合物UO₂(NO₃)₂·N₂O₄。
