A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninskiy pr., Moscow, 119991, Russia.
Inorg Chem. 2010 Mar 1;49(5):2077-82. doi: 10.1021/ic901526e.
A new mixed valent neptunium compound BuMeIm[Np(NpO(2))(3)(H(2)O)(6)Cl(12)] was synthesized by evaporation of an ethyl acetate-acetone mixture where the salt BuMeIm[NpCl(6)] was dissolved. The crystal structure was determined using single crystal X-ray diffraction; it consists of four crystallographically unique Np centers with two different coordination environments in two different oxidation states. In addition, five crystallographically independent dialkylimidazolium cations stabilize the crystal through C-H...Cl hydrogen bonds. [Np(NpO(2))(3)(H(2)O)(6)Cl(12)] unit presents a highly symmetric structure with the formation of three Np(IV)-Np(V)O(2)(+) bonds. According to the crystal structure and density functional theory (DFT) calculations, the stability of the three Np(4+)-NpO(2)(+) interactions is due to the presence of chloride ions around NpO(2)(+) which brings electronic charge into the system and also to the presence of water molecules which create hydrogen bond with chloride ions.
一种新的混合价态的镎化合物BuMeIm[Np(NpO(2))(3)(H(2)O)(6)Cl(12)]通过蒸发溶解在BuMeIm[NpCl(6)]盐的乙酸乙酯-丙酮混合物中合成。利用单晶 X 射线衍射法确定了晶体结构；它由四个晶体学上独特的 Np 中心组成，具有两种不同的配体环境和两种不同的氧化态。此外，五个独立的二烷基咪唑阳离子通过 C-H…Cl 氢键稳定了晶体。[Np(NpO(2))(3)(H(2)O)(6)Cl(12)]单元呈现出高度对称的结构，形成了三个 Np(IV)-Np(V)O(2)(+)键。根据晶体结构和密度泛函理论（DFT）计算，三个 Np(4+)-NpO(2)(+)相互作用的稳定性是由于 NpO(2)(+)周围存在氯离子，这将电子电荷带入系统，以及水分子与氯离子形成氢键。
