Fryer-Kanssen Izaak, Malcomson Thomas, Austin Jonathan, Kerridge Andrew
Department of Chemistry, Lancaster University, Bailrigg, Lancaster, LA1 4YB, UK.
Department of Chemistry, School of Natural Sciences, University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
Phys Chem Chem Phys. 2023 Jul 26;25(29):19453-19461. doi: 10.1039/d3cp01832f.
We compare the stabilities and bonding nature of [Eu/Am(BTPhen)(NO)] complexes to those previously reported for [Eu/Am(BTP)], and investigate whether more accurately reflecting the reaction conditions of the separation process by considering [Eu/Am(NO)(HO)] ( = 3, 4) complexes instead of aquo complexes increases the selectivity of the separation ligands BTP and BTPhen for Am over Eu. The geometric and electronic structures of [Eu/Am(BTPhen)(NO)] and [Eu/Am(NO)(HO)] ( = 3, 4) have been evaluated using density functional theory (DFT) and used as the basis for analysis of the electron density through the application of the quantum theory of atoms in molecules (QTAIM). Increased covalent bond character for the Am complexes of BTPhen over Eu analogues was found, with this increase more pronounced than that found in BTP complexes. BHLYP-derived exchange reaction energies were evaluated using the hydrated nitrates as a reference and a favourability for actinide complexation by both BTP and BTPhen was found, with the BTPhen ligand found to be more selective, with relative stability ≈0.17 eV greater than BTP.
我们将[Eu/Am(BTPhen)(NO)]配合物的稳定性和键合性质与之前报道的[Eu/Am(BTP)]的稳定性和键合性质进行比较，并研究通过考虑[Eu/Am(NO)(H₂O)]ₙ（n = 3, 4）配合物而非水合配合物来更准确地反映分离过程的反应条件是否会提高分离配体BTP和BTPhen对Am相对于Eu的选择性。已使用密度泛函理论（DFT）评估了[Eu/Am(BTPhen)(NO)]和[Eu/Am(NO)(H₂O)]ₙ（n = 3, 4）的几何和电子结构，并将其用作通过应用分子中原子的量子理论（QTAIM）分析电子密度的基础。发现BTPhen的Am配合物相对于Eu类似物具有更高的共价键特征，且这种增加比在BTP配合物中发现的更明显。以水合硝酸盐为参考评估了BHLYP衍生的交换反应能，发现BTP和BTPhen对锕系元素均具有形成配合物的倾向，且发现BTPhen配体更具选择性，其相对稳定性比BTP大约0.17 eV。
Zotero 插件