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

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [1];  [2];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Florida State Univ., Tallahassee, FL (United States)
+ Show Author Affiliations
Covalency is often considered to be an influential factor in driving An3+ vs. Ln3+ selectivity invoked by soft donor ligands. This is intensely debated, particularly the extent to which An3+/Ln3+ covalency differences prevail and manifest as the f-block is traversed, and the effects of periodic breaks beyond Pu. In this work, 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.
Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC)
Grant/Contract Number:
89233218CNA000001; AC52-06NA25396; SC0016568
OSTI ID:
1782645
Alternate ID(s):
OSTI ID: 1782988
OSTI ID: 23006326
Report Number(s):
LA-UR--21-20831
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 17 Vol. 60; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Structural and Spectroscopic Comparison of Soft‐Se vs. Hard‐O Donor Bonding in Trivalent Americium/Neodymium Molecules
Journal Article · Tue Mar 09 19:00:00 EST 2021 · Angewandte Chemie · OSTI ID:3023986

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
actinides
americium
covalency
spectroscopy
structure