Understanding the Complexation of Alkyl-Substituted Nitrilotriacetamides with Uranium: A Study by Absorption Spectroscopy and Microcalorimetry.
Inorg Chem
; 63(24): 11270-11278, 2024 Jun 17.
Article
em En
| MEDLINE
| ID: mdl-38842429
ABSTRACT
Complexation thermodynamics of UO22+ ions with a series of alkyl-substituted nitrilotriacetamides (NTA) was investigated by absorption spectroscopy and microcalorimetry. The hexamethyl derivative of NTA (HMNTA) forms the weakest two successive complexes with UO22+ ions with stability constants of log ß11 = 3.5 ± 0.1 and log ß12 = 6.1 ± 0.1. The formation constant values increased linearly with increasing alkyl chain length of the substituents from hexamethyl NTA to hexabutyl NTA (HBNTA) and to hexahexyl NTA (HHNTA). The complexation with each ligand was both enthalpy and entropy driven with exothermic enthalpy changes of ΔH11 = -14.7 ± 1.0 kJ/mol, ΔH12 = -10.2 ± 0.8 kJ/mol for HMNTA, ΔH11 = -19.2 ± 1.2 kJ/mol, ΔH12 = -16.4 ± 1.1 kJ/mol for HBNTA, and ΔH11 = -21.3 ± 1.4 kJ/mol, ΔH12 = -19.4 ± 2.3 kJ/mol for HHNTA. Similarly, the positive entropy changes with each ligand were ΔS11 = 18.1 ± 2.7 J/mol/K, ΔS12 = 82.9 ± 3.8 J/mol/K for HMNTA, ΔS11 = 14.4 ± 1.2 J/mol/K, ΔS12 = 87.2 ± 4.2 J/mol/K for HBNTA, and ΔS11 = 16.1 ± 2.4 J/mol/K, ΔS12 = 92.6 ± 3.1 J/mol/K for HHNTA. Structural features of the complex suggest the participation of two ligands coordinating in a bidentate mode via the carbonyl oxygens. The [UO2L2]2+ complexes appear to be noncentrosymmetric with two ligands and one water molecule occupying the equatorial plane of the dioxo uranyl cation. The structure of the complex was confirmed by 1H NMR titration, EXAFS measurements, and DFT calculations.
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01-internacional
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MEDLINE
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En
Ano de publicação:
2024
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Article