IR fingerprints of U(VI) nitrate monoamides complexes: a joint experimental and theoretical study.

6533b821fe1ef96bd127aea3

RESEARCH PRODUCT

IR fingerprints of U(VI) nitrate monoamides complexes: a joint experimental and theoretical study.

Catherine Rabbe Antonio Prestianni Marie-christine Charbonnel Laurent Joubert Carlo Adamo Gérard Cote Marie-noelle Ohnet Alexandre Chagnes

subject

Theoretical study Electron density Topological analysis Engineering controlled terms: Dimethylformamide Inorganic chemistry DFT calculation Strontium compound chemistry.chemical_element Infrared spectroscopy Ligand 010402 general chemistry Topology 01 natural sciences Electrostatic interaction Spectral line chemistry.chemical_compound Delocalized electron Nitrate Positive charge [CHIM]Chemical Sciences Physical and Theoretical Chemistry Electron densitie Infrared spectrum Spectroscopy ComputingMilieux_MISCELLANEOUS Ligand molecule 010405 organic chemistry Sulfur compound Uranium Toluene N N-Dimethylformamide 0104 chemical sciences Stable complexe [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry chemistry Organic solvent Uranium Physical chemistry Degree of polarization Degree of polarization Monoamide Uranium compounds Engineering main heading: Complexation Toluene

description

Infrared spectra of 0.5 mol·L-1 uranium(VI) nitrate monoamide complexes in toluene have been recorded and compared with infrared spectra calculated by DFT. The investigated monoamides were N,N- dimethylformamide (DMF), N,N-dibutylformamide (DBF), and N,N- dicyclohexylformamide (DcHF). The validity of DFT calculations for describing uranium nitrate monoamide complexes has been confirmed as a fair agreement between experimental and calculated spectra was obtained. Furthermore, a topological analysis of the electron density has been carried out to characterize monoamide-uranium interactions. From this work, it appears that the increase of stability of uranylmonoamide complexes may be directly linked to the degree of polarization of the ligands in interaction with uranylnitrate. Among the investigated monoamides, the most stable complex is UO 2(NO3)2·2DcHF. This complex is characterized by a high positive charge delocalization in the outer part of the ligand molecule, which leads to a more concentrated positive charge close to the uranyl cation (UO22+), thus strengthening the electrostatic interaction between the metal and the ligand. © 2010 American Chemical Society.

year	journal	country	edition	language
2010-10-14	The journal of physical chemistry. A

10.1021/jp106467p https://pubmed.ncbi.nlm.nih.gov/20858001