The solution structures and relative stability constants of lanthanide–EDTA complexes predicted from computation

O’Brien, Ravi D.; Summers, Thomas J.; Kaliakin, Danil S.; Cantu, David C.

doi:10.1039/d2cp01081j

Title: The solution structures and relative stability constants of lanthanide–EDTA complexes predicted from computation

Journal Article · 05 April 2022 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/d2cp01081j · OSTI ID:1870894

O’Brien, Ravi D. ^[1];

^[1];

^[1]

Univ. of Nevada, Reno, NV (United States)

Ligand selectivity to specific lanthanide (Ln) ions is key to the separation of rare earth elements from each other. Ligand selectivity can be quantified with relative stability constants (measured experimentally) or relative binding energies (calculated computationally). The relative stability constants of EDTA (ethylenediaminetetraacetic acid) with La³⁺, Eu³⁺, Gd³⁺, and Lu³⁺ were predicted from relative binding energies, which were quantified using electronic structure calculations with relativistic effects and based on the molecular structures of Ln–EDTA complexes in solution from density functional theory molecular dynamics simulations. The protonation state of an EDTA amine group was varied to study pH ~7 and ~11 conditions. Further, simulations at 25 °C and 90 °C were performed to elucidate how structures of Ln–EDTA complexes varying with temperature are related to complex stabilities at different pH conditions. Relative stability trends are predicted from computation for varying Ln³⁺ ions (La, Eu, Gd, Lu) with a single ligand (EDTA at pH ~11), as well as for a single Ln³⁺ ion (La) with varying ligands (EDTA at pH ~7 and ~11). Changing the protonation state of an EDTA amine site significantly changes the solution structure of the Ln–EDTA complex resulting in a reduction of the complex stability. As a result, increased Ln–ligand complex stability is correlated to reduced structural variations in solution upon an increase in temperature.

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Research Organization:: Univ. of Nevada, Reno, NV (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); USDOE

Grant/Contract Number:: SC0022178; Award Number DE-SC0022178

OSTI ID:: 1870894

Alternate ID(s):: OSTI ID: 1863616

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 24, Issue 17; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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