title: A DFT and experimental investigation of the electron affinity of the triscyclopentadienyl uranium complexes Cp3UX.
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.
authors.affiliation: Laboratoire de physique et chimie quantique, Faculté des sciences, Université Mouloud Mammeri de Tizi-Ouzou, 15000 Tizi-Ouzou, Algérie.
authors.forename: Aziz
authors.initials: A
authors.lastname: Elkechai
authors.forename: Abdou
authors.initials: A
authors.lastname: Boucekkine
authors.forename: Lotfi
authors.initials: L
authors.lastname: Belkhiri
authors.forename: Mhand
authors.initials: M
authors.lastname: Amarouche
authors.forename: Caroline
authors.initials: C
authors.lastname: Clappe
authors.forename: Didier
authors.initials: D
authors.lastname: Hauchard
authors.forename: Michel
authors.initials: M
authors.lastname: Ephritikhine