Structural Trends and Vibrational Analysis of N,N,N′,N′−Tetramethylmalonamide Complexes Across the Lanthanide Series

Kravchuk, Dmytro V.; Wang, Xiaoyu; Servis, Michael J.; Wilson, Richard E.

doi:10.1002/ejic.202300632

Structural Trends and Vibrational Analysis of N,N,N′,N′−Tetramethylmalonamide Complexes Across the Lanthanide Series

Journal Article · Wed Jan 31 00:00:00 EST 2024 · European Journal of Inorganic Chemistry

DOI:https://doi.org/10.1002/ejic.202300632· OSTI ID:2481050

^[1]; Wang, Xiaoyu ^[1]; Servis, Michael J. ^[1]; ^[1]

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

Fundamental understanding of coordination chemistry across the lanthanide series is essential for explaining chemical behavior of rare-earth metals in complex liquid-liquid extraction processes, which in turn affects the distribution ratios and efficacy of separations as a whole. In this work, we explore the structural trends between the lanthanides and a neutral N,N,N',N'-tetramethylmalonamide (TMMA) ligand within four isolated families of solid-state compounds: Ln(trans-TMMA)₂(NO₃)₃ Ln=La-Nd, Sm; Ln(cis-TMMA)₂(NO₃)₃ Ln=Eu-Tb, Er; [Ln(TMMA)₃(NO₃)₂][Ln(TMMA)(NO₃)₄] Ln=Dy-Tm; Ln(Κ²-TMMA)(iPrOH)(NO₃)₃ and Ln(Κ¹-TMMA)(Κ²-TMMA)(NO₃)₃ Ln=Yb, Lu. Moving across the lanthanide series, we note the formation of both discrete charge-neutral complexes, as well as charged molecular anion-cation pairs, with variations in spatial ligand arrangement, coordination numbers, and ligand denticities. IR and Raman spectroscopy paired with DFT frequency calculations were used for an in-depth investigation of vibrational modes unique to each structural family. The collection of isolated model compounds was also discussed in the context of liquid-liquid separations based on reported distribution ratios from malonamide extraction.

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:: 2481050

Journal Information:: European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry Journal Issue: 6 Vol. 27; ISSN 1434-1948

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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