Activation of Actinyls to Generate Actinide ...
Type de document :
Autre communication scientifique (congrès sans actes - poster - séminaire...)
Titre :
Activation of Actinyls to Generate Actinide Nitridos, which Activate CO<sub>2</sub> to Regenerate the Actinyls
Auteur(s) :
Parker, Mariah [Orateur]
Chemical Sciences Division [LBNL Berkeley] [CSD]
Gong, Yu [Auteur]
Chemical Sciences Division [LBNL Berkeley] [CSD]
Gibson, John K. [Auteur]
Chemical Sciences Division [LBNL Berkeley] [CSD]
Vallet, Valérie [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Chemical Sciences Division [LBNL Berkeley] [CSD]
Gong, Yu [Auteur]
Chemical Sciences Division [LBNL Berkeley] [CSD]
Gibson, John K. [Auteur]
Chemical Sciences Division [LBNL Berkeley] [CSD]
Vallet, Valérie [Auteur]
![refId](/themes/Mirage2//images/idref.png)
Physico-Chimie Moléculaire Théorique [PCMT]
Titre de la manifestation scientifique :
Inorganic Chemistry Gordon Research Conference
Ville :
Newport, Ri
Pays :
Etats-Unis d'Amérique
Date de début de la manifestation scientifique :
2020-05-31
Date de publication :
2020-05-31
Discipline(s) HAL :
Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
Résumé en anglais : [en]
Gas-phase reactions of actinide complexes enlarge the scope of accessible chemistry of these elements, and provide insights into bond activation that may be unattainable or incomprehensible in condensed phases. The distinctive ...
Lire la suite >Gas-phase reactions of actinide complexes enlarge the scope of accessible chemistry of these elements, and provide insights into bond activation that may be unattainable or incomprehensible in condensed phases. The distinctive actinyl moieties—hexavalent An<sup>VI</sup>O<sub>2</sub><sup>2+</sup> and pentavalent An<sup>V</sup>O<sub>2</sub><sup>+</sup>, where An = Pa, U, Np, Pu or Am—present robust oxo bonds that are particularly resistant to activation. Actinyl activation by isocyanate ligands in anionic complexes has been achieved by endothermic reactions (1) and (2).[U<sup>VI</sup>O<sub>2</sub>Cl<sub>2</sub>(NCO)]<sup>-</sup> → [NU<sup>VI</sup>OCl<sub>2</sub>]<sup>-</sup> + CO<sub>2</sub> (1)<br>[Np<sup>V</sup>O<sub>2</sub>Cl(NCO)]<sup>-</sup> → [NNp<sup>V</sup>OCl]<sup>-</sup> + CO<sub>2</sub> (2)<br>The computed potential energy profile for reaction (1) predicted that the reverse reaction should occur in the absence of excitation. Remarkably, it was demonstrated that the uranium nitrido does indeed spontaneously activate CO<sub>2</sub> to regenerate uranyl. A central goal in actinide chemistry is to identify and understand variations across the series. Reaction (2) is evidently more facile than (1), which may reflect stronger U=O versus Np=O bonds, and furthermore indicates lower kinetic barriers to activation of neptunyl(V) versus uranyl(VI). Relativistic multireference computations are underway to understand this difference in reactivity. Other experimental/computational targets include activation of plutonyl(V/VI) and americyl(V) for comparison with the lighter congeners, and ultimately to provide guidance for condensed phase synthesis.Lire moins >
Lire la suite >Gas-phase reactions of actinide complexes enlarge the scope of accessible chemistry of these elements, and provide insights into bond activation that may be unattainable or incomprehensible in condensed phases. The distinctive actinyl moieties—hexavalent An<sup>VI</sup>O<sub>2</sub><sup>2+</sup> and pentavalent An<sup>V</sup>O<sub>2</sub><sup>+</sup>, where An = Pa, U, Np, Pu or Am—present robust oxo bonds that are particularly resistant to activation. Actinyl activation by isocyanate ligands in anionic complexes has been achieved by endothermic reactions (1) and (2).[U<sup>VI</sup>O<sub>2</sub>Cl<sub>2</sub>(NCO)]<sup>-</sup> → [NU<sup>VI</sup>OCl<sub>2</sub>]<sup>-</sup> + CO<sub>2</sub> (1)<br>[Np<sup>V</sup>O<sub>2</sub>Cl(NCO)]<sup>-</sup> → [NNp<sup>V</sup>OCl]<sup>-</sup> + CO<sub>2</sub> (2)<br>The computed potential energy profile for reaction (1) predicted that the reverse reaction should occur in the absence of excitation. Remarkably, it was demonstrated that the uranium nitrido does indeed spontaneously activate CO<sub>2</sub> to regenerate uranyl. A central goal in actinide chemistry is to identify and understand variations across the series. Reaction (2) is evidently more facile than (1), which may reflect stronger U=O versus Np=O bonds, and furthermore indicates lower kinetic barriers to activation of neptunyl(V) versus uranyl(VI). Relativistic multireference computations are underway to understand this difference in reactivity. Other experimental/computational targets include activation of plutonyl(V/VI) and americyl(V) for comparison with the lighter congeners, and ultimately to provide guidance for condensed phase synthesis.Lire moins >
Langue :
Anglais
Comité de lecture :
Oui
Audience :
Internationale
Vulgarisation :
Non
Projet ANR :
Source :