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Article Dans Une Revue Journal- Chemical Society Dalton Transactions Année : 2009

A DFT and experimental investigation of the electron affinity of the triscyclopentadienyl uranium complexes Cp3UX

Résumé

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 Cp3UX (X = Cl, BH4, SPh, SiPr and OiPr) related to the U(IV)/U(III) redox system. E1/2 half-wave potentials have been measured in solution (THF) under the same rigorous conditions for all the species under consideration. A good correlation (r2 = 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.

Domaines

Chimie organique
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Dates et versions

hal-00389602 , version 1 (12-09-2013)

Identifiants

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Aziz Elkechai, Abdou Boucekkine, Lotfi Belkhiri, Mhand Amarouche, Caroline Clappe, et al.. A DFT and experimental investigation of the electron affinity of the triscyclopentadienyl uranium complexes Cp3UX. Journal- Chemical Society Dalton Transactions, 2009, 15, pp.2843-2849. ⟨10.1039/b820873e⟩. ⟨hal-00389602⟩
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