Structural and Spectroscopic Comparison of Soft-Se vs. Hard-O Donor Bonding in Trivalent Americium/Neodymium Molecules

被引：27

作者：

Goodwin, Conrad A. P. ^{[1
]}

Schlimgen, Anthony W. ^{[2
]}

Albrecht-Schonzart, Thomas E. ^{[3
]}

Batista, Enrique R. ^{[2
]}

Gaunt, Andrew J. ^{[1
]}

Janicke, Michael T. ^{[1
]}

Kozimor, Stosh A. ^{[1
]}

Scott, Brian L. ^{[4
]}

Stevens, Lauren M. ^{[1
]}

White, Frankie D. ^{[1
]}

Yang, Ping ^{[2
]}

机构：

[1] Los Alamos Natl Lab, Chem Div, Los Alamos, NM 87545 USA

[2] Los Alamos Natl Lab, Theoret Div, Los Alamos, NM 87545 USA

[3] Florida State Univ, Dept Chem & Biochem, 95 Chieftain Way, Tallahassee, FL 32306 USA

[4] Los Alamos Natl Lab, Mat Phys & Applicat Div, Los Alamos, NM 87545 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2021年 / 60卷 / 17期

关键词：

actinides; americium; covalency; spectroscopy; structure; STATE PERTURBATION-THEORY; ELECTRONIC-ENERGY LEVELS; COMPLEXES; COVALENCY; AMERICIUM; ACTINIDE; ELEMENT; LIGAND; SEPARATION; IMPLEMENTATION;

D O I：

10.1002/anie.202017186

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Covalency is often considered to be an influential factor in driving An(3+) vs. Ln(3+) selectivity invoked by soft donor ligands. This is intensely debated, particularly the extent to which An(3+)/Ln(3+) 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=PPh2)(2)}(3)] (1-Am, E=Se; 2-Am, E=O) are compared to isoradial [Nd{N(E=PPh2)(2)}(3)] (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.

引用

页码：9459 / 9466

页数：8