Abstract:
In this work, we present a relativistic DFT study of a family of uranium complexes Cp2U(=NAr)X, (UVI/UV/UVI) and Cp2U[N(TMS)2]X, (UIII/UIV/UV), associated with functionalized ligands X type and / or donor. These compounds, whose X-ray structure of some of them is known, have not been the subject of any theoretical study to date. We will particularly study molecular geometries, the relationship between electronic structure and redox behavior and the nature of the metal-ligand interactions involved. We will analyze the different possible correlations between the values of the calculated quantum quantities (EA, IE, net metal charge, HOMO/LUMO and bond indices) with the variations of the half-wave redox potential (-E1/2) measured experimentally. As part of the predictive aspet of the DFT method, we will analyze the redox properties of some unknown or not yet isolated species. These series, were synthesized by the group of Kiplinger et al, and whose X-ray structures and electrochemical data, are known for most compounds, as illustrated on the figure. The FTD calculation method used is based on the ZORA/COSMO+SO approach conducted using the ADF code. Relativistic calculations, taking into account solvent effects and spinorbit coupling, led to a good correlation AE(eV) vs. -E1/2 (V) with a factor R2 > 0.97 in good agreement with the bibliographic data, testifying to the robust model used.
