Valérie Vallet
@valevallet.bsky.social
63 followers
98 following
6 posts
CNRS researcher in theoretical and computational chemistry
PhLAM institute @univlille.bsky.social
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Valérie Vallet
@valevallet.bsky.social
· Aug 19
Reactions of Np(VI) and Pu(VI) with Phenanthroline Result in Bending the [NpVIO2]2+ Unit and a Reduced Pu(V) Species
Despite decades of actinyl chemistry, genuinely bent actinyl structures remain rare beyond uranium. We report the first crystallographic characterization of a bent neptunyl(VI) complex, NpO2Cl2(phen)2, along with a linear plutonyl species that, unexpectedly, adopts the +V oxidation state. Coordination of two 1,10-phenanthroline ligands to NpO22+ enforces pronounced bending of the Oyl–Np–Oyl unit to 162° through steric clashes with the axial phenathroline ligand, representing the sharpest angle reported for any neptunyl(VI) complex. In contrast, synthesis with PuO22+ produces a reduced linear Pu(V) species, PuO2Cl(phen)2, underscoring the redox lability and the reluctance of plutonium to distort. Raman and IR spectra yield the first experimental stretching and interaction force constants for plutonyl(V). Comparison with values for plutonyl(VI) and bent and linear uranyl(VI) and neptunyl(VI) compounds shows that reduction perturbs the actinyl bond more than bending within one oxidation state. Electrochemical and spectroscopic studies clarify phenanthroline binding to Pu(VI) and the system’s reactivity. Quantum chemical calculations indicate that bending is energetically favored in the U–Np–Pu series, but the stabilization energy decreases as the actinide atomic number increases. NBO and QTAIM analyses reveal systematic trends: increasing 5f occupancy and decreasing An–Oyl bond covalency from U to Pu. These results demonstrate that ligand-induced bending in neptunyl(VI) species is not only electronically feasible but also synthetically achievable, though plutonyl(VI) is constrained by redox reactivity. This work expands the frontier of nonlinear actinyl chemistry and illuminates how structure, oxidation state, and electronic configuration interrelate across the actinyl series.
doi.org
Valérie Vallet
@valevallet.bsky.social
· Jun 18
U4+ Speciation in Acidic Aqueous Solution: Insights from UV–Vis, EXAFS, XANES, and Quantum-Statistical Simulations
This theoretical study investigates the UV–vis absorption properties of U4+-containing aqueous solutions and their relationship with the nature of aqua-complexes present at varying acidic levels. High...
doi.org
Reposted by Valérie Vallet
Valérie Vallet
@valevallet.bsky.social
· Jan 31
Antton Rouget
@anttonrouget.bsky.social
· Jan 30
Pierre-Édouard Stérin sort le carnet de chèques pour faire gagner la droite de la droite dans les têtes et dans les urnes - LA LETTRE
Alerte publiée le 30/01/25 à 17 h 58 - De Contribuables Associés au très droitier Institut de formation politique, en passant par le lobby patronal de Sophie de Menthon, le milliardaire catholique
www.lalettre.fr
Reposted by Valérie Vallet
Bitsy Perlman
@bitsyperlman.bsky.social
· Jan 30
Reposted by Valérie Vallet
Pr. Logos
@prlogos.bsky.social
· Jan 30
Reposted by Valérie Vallet
Reposted by Valérie Vallet
Carl T. Bergstrom
@carlbergstrom.com
· Jan 27