Abstract
| Lingua originale | English |
|---|---|
| pagine (da-a) | 10878-10884 |
| Numero di pagine | 7 |
| Rivista | JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY |
| Volume | 114 |
| Stato di pubblicazione | Published - 2010 |
Fingerprint
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
Cita questo
IR fingerprints of U(VI) nitrate monoamides complexes: A joint experimental and theoretical study. / Prestianni, Antonio; Prestianni, Antonio; Chagnes, Alexandre; Charbonnel, Marie-Christine; Rabbe, Catherine; Joubert, Laurent; Adamo, Carlo; Ohnet, Marie-Noelle; Cote, Gerard.
In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY, Vol. 114, 2010, pag. 10878-10884.Risultato della ricerca: Article
}
TY - JOUR
T1 - IR fingerprints of U(VI) nitrate monoamides complexes: A joint experimental and theoretical study
AU - Prestianni, Antonio
AU - Prestianni, Antonio
AU - Chagnes, Alexandre
AU - Charbonnel, Marie-Christine
AU - Rabbe, Catherine
AU - Joubert, Laurent
AU - Adamo, Carlo
AU - Ohnet, Marie-Noelle
AU - Cote, Gerard
PY - 2010
Y1 - 2010
N2 - 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.
AB - 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.
KW - Degree of polarization; DFT calculation; Electron densities; Electrostatic interactions; Infrared spectrum; Ligand molecules; Monoamides; N
KW - N-Dimethylformamide; Positive charges; Stable complexes; Theoretical study; Topological analysis Engineering controlled terms: Dimethylformamide; Ligands; Organic solvents; Spectroscopy; Strontium compounds; Sulfur compounds; Toluene; Topology; Uranium; U
UR - http://hdl.handle.net/10447/54068
M3 - Article
VL - 114
SP - 10878
EP - 10884
JO - JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY
JF - JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY
SN - 1089-5639
ER -