Klamm Bonnie E, Windorff Cory J, Celis-Barros Cristian, Beltran-Leiva Maria J, Sperling Joseph M, Albrecht-Schönzart Thomas E
Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Room 118 DLC, Tallahassee, Florida 32306, United States.
Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87544, United States.
Inorg Chem. 2020 Dec 21;59(24):18035-18047. doi: 10.1021/acs.inorgchem.0c02455. Epub 2020 Nov 25.
A pair of neptunium Schiff base coordination complexes, and { = ,'-bis[(4,4'-diethylamino)salicylidene]-1,2-phenylenediamine}, have been synthesized and analyzed by several characterization methods including single-crystal X-ray diffraction, electronic absorption, H NMR, cyclic voltammetry, and theoretical interpretation. Structural analysis reveals that and are isomorphous with the previously reported and (M = Pu, Ce, U, Th) complexes, respectively, allowing for a direct comparison across the series. The reduction of or direct synthesis from a (NpO) source shows evidence of a pentavalent neptunyl species as determined by UV/vis/NIR and H NMR spectroscopy. The synthesis of directly from a (NpO) starting material gives a similar spectrum. Theoretical analysis offers insight into the electronic structure for a better understanding of the bonding patterns and relative stability of the different oxidation states. Computational results show that the Np-L covalent interactions in are similar to those in the complex, indicating that neither the presence of the axial oxo ligands nor the oxidation state significantly modify the nature of the Np-L bonds.
合成了一对镎席夫碱配位络合物 和 { = ，'-双[(4,4'-二乙氨基)水杨叉]-1,2-苯二胺}，并通过包括单晶X射线衍射、电子吸收、核磁共振氢谱、循环伏安法和理论解释在内的多种表征方法进行了分析。结构分析表明， 和 分别与先前报道的 和 （M = Pu、Ce、U、Th）络合物同构，从而可以对整个系列进行直接比较。由紫外/可见/近红外光谱和核磁共振氢谱测定，由 还原或从（NpO）源直接合成显示出五价镎酰 物种的证据。直接从（NpO）起始原料合成 得到了相似的光谱。理论分析为更好地理解不同氧化态的键合模式和相对稳定性提供了对电子结构的深入了解。计算结果表明， 中Np-L共价相互作用与 络合物中的相似，表明轴向氧配体的存在和氧化态均未显著改变Np-L键的性质。
