Synthesis and characterization of the rare-earth chloride complexes with N,N,N',N'-tetramethylmalonamide

Kravchuk, Dmytro V.; Wilson, Richard E.

doi:10.1016/j.jssc.2024.124595

Synthesis and characterization of the rare-earth chloride complexes with N,N,N',N'-tetramethylmalonamide

Journal Article · Sat Feb 03 00:00:00 EST 2024 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2024.124595· OSTI ID:2310370

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Argonne National Laboratory (ANL), Argonne, IL (United States)

Exploration of the solid-state chemistry of the f-elements and their coordination chemistry can assist in understanding the speciation of these elements in solution, which, in turn, can aid in the interpretation of their chemical behavior in complex liquid-liquid separations. Within these separation processes, malonamides are common organic extractants that are used for complexing both lanthanides and actinides, thus it is relevant to understand the malonamide ligand complexation under various conditions. In this work, we investigate solid-state complexes of the rare-earth chlorides with N,N,N',N'-tetramethylmalonamide (TMMA) across the entire lanthanide series. Here, we isolated two structural families of compounds Ln(TMMA)₂Cl₃ Ln = La–Dy and [Ln(TMMA)₂(H₂O)₄]Cl₃ • xH₂O x = 0,4 Ln = Ho–Lu, showing differences in chloride coordination from the inner-sphere complex for early lanthanides to outer-sphere for the late lanthanides. Both structural series were additionally analyzed by both IR and Raman spectroscopy confirming similarities in malonamide ligand coordination modes, while showing differences in vibrational features associated with chloride and aqua ligand coordination.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2310370

Journal Information:: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Vol. 332; ISSN 0022-4596

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Synthesis and characterization of the rare-earth chloride complexes with N,N,N',N'-tetramethylmalonamide

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