Selectivity of Azine Ligands Toward Lanthanide(III)/Actinide(III) Differentiation: A Relativistic DFT Based Rationalization
| Autor: | Abdellah Zaiter, Lotfi Belkhiri, Abdou Boucekkine, Boudersa Amine, Michel Ephritikhine, Yamina Bouzidi |
|---|---|
| Přispěvatelé: | Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Service Interdisciplinaire sur les Systèmes Moléculaires et les Matériaux (ex SCM) (SIS2M UMR 3299), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2014 |
| Předmět: |
Lanthanide
education.field_of_study 010405 organic chemistry Ligand Chemistry Population Actinide 010402 general chemistry Highly selective 01 natural sciences 0104 chemical sciences Inorganic Chemistry Azine [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Crystallography chemistry.chemical_compound Computational chemistry Molecule Physical and Theoretical Chemistry education Selectivity |
| Zdroj: | Inorganic Chemistry Inorganic Chemistry, American Chemical Society, 2014, 53 (9), pp.4687-4697. ⟨10.1021/ic500361b⟩ Inorganic Chemistry, 2014, 53 (9), pp.4687-4697. ⟨10.1021/ic500361b⟩ |
| ISSN: | 0020-1669 1520-510X |
| DOI: | 10.1021/ic500361b⟩ |
| Popis: | Polyazines emerge as highly selective ligands toward actinide versus lanthanide separation. Electronic structures of several mono- and polyazine f-complexes of general formula MX3L (M(+3) = Ce, Nd, Eu, U, Am, and Cm; X = RCp(-) or NO3(-); L = N-donor ligand) related to Ln(III)/An(III) differentiation have been investigated using scalar relativistic ZORA/DFT calculations. In all cases, DFT calculations predict shorter An-N bonds than Ln-N ones whatever the azine used, in good agreement with available experimental data. The An-N bonds are also characterized by higher stretching frequencies than Ln-N bonds. The electronic structures of all species have been studied using different population analyses, among them natural population (NPA) and the quantum theory of atoms in molecule approach (QTAIM), as well as using different bond indices. The ability for Ln(III)/An(III) differentiation of the terdentate bipyrazolate BPPR ligand in the M(BPPR)(NO3)3 complexes (M(3+) = Ce, Eu, U and Am ; R = H, 2,2-dimethylpropyl) where BPP = 2,6-bis(dialkyl-1H-pyrazol-3-yl)pyridine has been studied, with a special emphasis on the total metal-ligand bonding energy (TBE). The ZORA/DFT approach was found to properly reproduce the higher selectivity of the polyazine BPP ligand compared to monoazines, especially for the Eu(III)/Am(III) pair operating in spent nuclear fuel, using computed TBEs as criterion. Moreover, the orbital part of the total bonding energy appears also to rationalize well the observed selectivity. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|