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Structural and Spectroscopic Comparison of Soft‐Se vs. Hard‐O Donor Bonding in Trivalent Americium/Neodymium Molecules
Author(s) -
Goodwin Conrad A. P.,
Schlimgen Anthony W.,
AlbrechtSchönzart 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
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202017186
Subject(s) - neodymium , americium , chemistry , crystallography , covalent bond , block (permutation group theory) , molecule , ab initio , spectroscopy , lanthanide , inorganic chemistry , ion , actinide , physics , organic chemistry , geometry , optics , laser , mathematics , quantum mechanics
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=PPh 2 ) 2 } 3 ] ( 1‐Am , E=Se; 2‐Am , E=O) are compared to isoradial [Nd{N(E=PPh 2 ) 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.