Abstract
Variations in bonding between trivalent lanthanides and actinides is critical for reprocessing spent nuclear fuel. The ability to tune bonding and the coordination environment in these trivalent systems is a key factor in identifying a solution for separating lanthanides and actinides. Coordination of 4,4′−bipyridine (4,4′−bpy) and trimethylsilylcyclopentadienide (Cp′) to americium introduces unexpectedly ionic Am−N bonding character and unique spectroscopic properties. Here we report the structural characterization of (Cp′3Am)2(μ − 4,4′−bpy) and its lanthanide analogue, (Cp′3Nd)2(μ − 4,4′−bpy), by single-crystal X-ray diffraction. Spectroscopic techniques in both solid and solution phase are performed in conjunction with theoretical calculations to probe the effects the unique coordination environment has on the electronic structure.
Highlights
Variations in bonding between trivalent lanthanides and actinides is critical for reprocessing spent nuclear fuel
The separation of minor trivalent actinides (An3+) from their lanthanide (Ln3+) counterparts is a crucial step in the reprocessing of spent nuclear fuels; this process remains a great challenge owing to similarities in oxidation state and ionic radii1–3
Recent advances in transuranic synthesis have yielded the structural characterization of organometallic plutonium and americium complexes17,19,20
Summary
Variations in bonding between trivalent lanthanides and actinides is critical for reprocessing spent nuclear fuel. The average M−Cent distance observed in 1-Am is shorter than those reported in similar multinuclear organometallic actinide systems, (Cp′′3Th)2(μ-4,4′bpy), 2.594(5) Å, and (Cp′3U)2(μ-4,4′-bpy), 2.540(10) Å14,39. Assuming that these pyridine-based ligands are valid comparisons, the greater M−N bond distances observed in 1-Nd and 1-Am are likely due to steric competition between the Cp′ rings and the bridging 4,4′-bpy.
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