Complexes organométalliques mono et polynucléaires d’actinides. Etude théorique DFT du mode de coordination métal-ligand et rôle des orbitales 5f

Abstract

The aim of this work, was to undertaken a theoretical study on electronic and magnetic properties of polynuclear uranium (V) and (IV) systems oxo-bridged synthesized by K. Meyer et al., and M. Mazzanti et al., for the two U(V) and U(IV) binuclear [{((nP,MeArO)3tacn)UV}2(μ-O)2, K2[{((nP,MeArO)3tacn)UIV}2(μ-O)2] complexes, and the pentavalent dioxo [UO2(dbm)2K(18C6)]2 and trioxo [UO2(L)]3 analogous. All computations were undertaken using the relativistic density functional theory (DFT), coupled with the broken symmetry (BS) approach and the hybrid B3LYP method. Our DFT/ZORA/BS/B3LYP recipe, despite its limits, has predicted satisfactory the Ferro and antiferromagnetic exchange coupling within such complexes in excellent agreement with experience.