Carpenter Stephanie H, Jones Margaret R, Lussier Daniel J, Gaunt Andrew J, Murillo Jesse, Tondreau Aaron M
Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States.
Inorg Chem. 2025 Apr 21;64(15):7263-7272. doi: 10.1021/acs.inorgchem.4c04433. Epub 2025 Apr 3.
A series of reactions using sodium bis(mesitoyl)phosphide () with the actinide starting material AnI(thf) (An = U, Np, Pu) as well as the analogous reaction with CeI(thf) was performed. Similar U and Np (An = U, Np) products were obtained in the +4-oxidation state. The thorium homologue was synthesized using ThI(dme) to generate , which was employed as a diamagnetic and predominantly redox inert metal center for comparison. The resulting product isolated from the analogous reaction with PuI(thf) was , where the metal coordinated four ligands and retained the +3-oxidation state. This result is distinct from that obtained from the reaction with CeI(thf), where the Ce product was . The compounds were isolated and characterized by X-ray diffraction, ultraviolet-visible (UV-vis)-nIR and NMR spectroscopies, and cyclic voltammetry. The synthetic results reveal how different redox stabilities across the 5f series can result in divergent reactivity of Pu. Electrochemical experiments produced redox features that suggest the potential to form reduced complexes supported by the BAP ligand framework.
使用双（均三甲酰基）磷化钠（）与锕系起始原料AnI（thf）（An = U、Np、Pu）进行了一系列反应，以及与CeI（thf）的类似反应。在 +4 氧化态下获得了类似的U和Np（An = U、Np）产物。使用ThI（dme）合成钍同系物以生成，将其用作抗磁性且主要为氧化还原惰性的金属中心进行比较。从与PuI（thf）的类似反应中分离出的产物是，其中金属配位了四个配体并保持 +3 氧化态。该结果与用CeI（thf）反应得到的结果不同，Ce产物是。通过X射线衍射、紫外可见（UV-vis）-近红外光谱和核磁共振光谱以及循环伏安法对这些化合物进行了分离和表征。合成结果揭示了5f系列中不同的氧化还原稳定性如何导致Pu的反应性不同。电化学实验产生的氧化还原特征表明，有可能形成由BAP配体框架支撑的还原配合物。
