Journal article
Europium, uranyl, and thorium-phenanthroline amide complexes in acetonitrile solution: an ESI-MS and DFT combined investigation
Dalton transactions : an international journal of inorganic chemistry, Vol.44(32), pp.14376-14387
2015
Handle:
https://hdl.handle.net/2376/106060
PMID: 26200662
Abstract
The tetradentate N,N′-diethyl-N,N′-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen) ligand with hard–soft donor atoms has been demonstrated to be promising for the group separation of actinides from highly acidic nuclear wastes. To identify the formed complexes of this ligand with actinides and lanthanides, electrospray ionization mass spectrometry (ESI-MS) combined with density functional theory (DFT) calculations was used to probe the possible complexation processes. The 1 : 2 Eu–L species ([EuL2(NO3)]2+) can be observed in ESI-MS at low metal-to-ligand ([M]/[L]) ratios, whereas the 1 : 1 Eu–L species ([EuL(NO3)2]+) can be observed when the [M]/[L] ratio is higher than 1.0. However, ([UO2L(NO3)]+) is the only detected species for the uranyl complexes. The [ThL2(NO3)2]2+ species can be observed at low [M]/[L] ratios; the 1 : 2 species ([ThL2(NO3)]3+) and a new 1 : 1 species ([ThL(NO3)3]+) can be detected at high [M]/[L] ratios. Collision-induced dissociation (CID) results showed that Et-Tol-DAPhen ligands can coordinate strongly with metal ions, and the coordination moieties remain intact under CID conditions. Natural bond orbital (NBO), molecular electrostatic potential (MEP), electron localization function (ELF), atoms in molecules (AIM) and molecular orbital (MO) analyses indicated that the metal–ligand bonds of the actinide complexes exhibited more covalent character than those of the lanthanide complexes. In addition, according to thermodynamic analysis, the stable cationic M–L complexes in acetonitrile are found to be in good agreement with the ESI-MS results.
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Details
- Title
- Europium, uranyl, and thorium-phenanthroline amide complexes in acetonitrile solution: an ESI-MS and DFT combined investigation
- Creators
- Cheng-Liang Xiao - School for Radiological and Interdisciplinary Sciences (RAD-X) and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, Suzhou 215123, China, Laboratory of Nuclear Energy Chemistry and Key Laboratory For Biomedical Effects of Nanomaterials and NanosafetyCong-Zhi Wang - Laboratory of Nuclear Energy Chemistry and Key Laboratory For Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, ChinaLei Mei - Laboratory of Nuclear Energy Chemistry and Key Laboratory For Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, ChinaXin-Rui Zhang - Laboratory of Nuclear Energy Chemistry and Key Laboratory For Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, ChinaNathalie Wall - Chemistry Department, Washington State University, Pullman 99164-4630, USAYu-Liang Zhao - Laboratory of Nuclear Energy Chemistry and Key Laboratory For Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, ChinaZhi-Fang Chai - School for Radiological and Interdisciplinary Sciences (RAD-X) and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, Suzhou 215123, China, Laboratory of Nuclear Energy Chemistry and Key Laboratory For Biomedical Effects of Nanomaterials and NanosafetyWei-Qun Shi - Laboratory of Nuclear Energy Chemistry and Key Laboratory For Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
- Publication Details
- Dalton transactions : an international journal of inorganic chemistry, Vol.44(32), pp.14376-14387
- Academic Unit
- Chemistry, Department of
- Identifiers
- 99900546739501842
- Language
- English
- Resource Type
- Journal article