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

Antonio Prestianni, Antonio Prestianni, Alexandre Chagnes, Marie-Christine Charbonnel, Catherine Rabbe, Laurent Joubert, Carlo Adamo, Marie-Noelle Ohnet, Gerard Cote

Risultato della ricerca: Article

11 Citazioni (Scopus)

Abstract

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.
Lingua originaleEnglish
pagine (da-a)10878-10884
Numero di pagine7
RivistaJOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY
Volume114
Stato di pubblicazionePublished - 2010

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Nitrates
uranium
nitrates
Uranium
Ligands
Discrete Fourier transforms
ligands
infrared spectra
Uranyl Nitrate
Infrared radiation
Dimethylformamide
Toluene
interactions
Coulomb interactions
Carrier concentration
toluene
Cations
Metals
Polarization
electrostatics

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

Prestianni, Antonio ; Prestianni, Antonio ; Chagnes, Alexandre ; Charbonnel, Marie-Christine ; Rabbe, Catherine ; Joubert, Laurent ; Adamo, Carlo ; Ohnet, Marie-Noelle ; Cote, Gerard. / IR fingerprints of U(VI) nitrate monoamides complexes: A joint experimental and theoretical study. In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY. 2010 ; Vol. 114. pagg. 10878-10884.
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abstract = "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. {\circledC} 2010 American Chemical Society.",
keywords = "Degree of polarization; DFT calculation; Electron densities; Electrostatic interactions; Infrared spectrum; Ligand molecules; Monoamides; N, 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; Uranium compounds Engineering main heading: Complexation",
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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

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