A DFT and experimental investigation of the electron affinity of the triscyclopentadienyl uranium complexes Cp3UX
Year: 2009
Type: article
Abstract: Relativistic Density Functional Theory (DFT) based methods coupled with the Conductor-like Screening Model (COSMO) for a realistic solvation approach are used to investigate the electron affinity (EA) of a series of triscyclopentadienyl uranium complexes Cp(3)UX (X = Cl, BH(4), SPh, S(i)Pr and O(i)Pr) related to the U(iv)/U(iii) redox system. E(1/2) half-wave potentials have been measured in solution (THF) under the same rigorous conditions for all the species under consideration. A good correlation (r(2) = 0.99) is found between the computed EA values, either in the gas phase or in solution, and the experimental half-wave potentials; the study brings to light the importance of spin-orbit coupling effects which must be taken into account in order to achieve the observed agreement between theory and experiment. The influence of the electron donating character of the X ligand on the orbital involved in the reduction process, namely the lowest unoccupied molecular orbital (LUMO) of the neutral U(iv) complexes, and on the EAs is discussed.
Source: Dalton Transactions
DOI: 10.1039/b820873e
Institutions: Centre National de la Recherche Scientifique, Institut des Sciences Chimiques de Rennes, Mouloud Mammeri University of Tizi-Ouzou, Université Rennes 1, Université de Rennes, Université Européenne de Bretagne, University Frères Mentouri Constantine 1, École Centrale Paris, École Nationale Supérieure de Chimie de Rennes, Commissariat à l'Énergie Atomique et aux Énergies Alternatives, Institut Rayonnement-Matière de Saclay, CEA Paris-Saclay
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W2018680450