Goodwin Conrad A P, Schlimgen Anthony W, Albrecht-Schönzart Thomas E, Batista Enrique R, Gaunt Andrew J, Janicke Michael T, Kozimor Stosh A, Scott Brian L, Stevens Lauren M, White Frankie D, Yang Ping
Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM, 87545, USA.
Theoretical Division, Los Alamos National Laboratory, Los Alamos, NM, 87545, USA.
Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9459-9466. doi: 10.1002/anie.202017186. Epub 2021 Mar 10.
Covalency is often considered to be an influential factor in driving An vs. Ln selectivity invoked by soft donor ligands. This is intensely debated, particularly the extent to which An /Ln covalency differences prevail and manifest as the f-block is traversed, and the effects of periodic breaks beyond Pu. Herein, two Am complexes, [Am{N(E=PPh ) } ] (1-Am, E=Se; 2-Am, E=O) are compared to isoradial [Nd{N(E=PPh ) } ] (1-Nd, 2-Nd) complexes. Covalent contributions are assessed and compared to U/La and Pu/Ce analogues. Through ab initio calculations grounded in UV-vis-NIR spectroscopy and single-crystal X-ray structures, we observe differences in f orbital involvement between Am-Se and Nd-Se bonds, which are not present in O-donor congeners.
共价性通常被认为是软供体配体引发锕系元素与镧系元素选择性的一个影响因素。这一点存在激烈争论，特别是在整个f区中锕系元素/镧系元素的共价性差异占主导并显现的程度，以及钚之后的周期中断的影响。在此，将两种镅配合物[Am{N(E=PPh ) } ]（1-Am，E = Se；2-Am，E = O）与等半径的[Nd{N(E=PPh ) } ]（1-Nd，2-Nd）配合物进行比较。评估共价贡献并与铀/镧和钚/铈类似物进行比较。通过基于紫外-可见-近红外光谱和单晶X射线结构的从头算计算，我们观察到镅-硒键和钕-硒键之间f轨道参与情况的差异，而在氧供体同系物中不存在这种差异。
