Experimental and Theoretical Comparison of Transition-Metal and Actinide Tetravalent Schiff Base Coordination...

A series of homoleptic tetravalent transition-metal and actinide Schiff-base coordination complexes, ML₂ {M = Zr, Hf, Th, U; L = N, N'-bis[(4,4'-diethylamino)salicylidene]-1,2-phenylenediamine}, have been synthesized that feature a rigid phenyl backbone. These complexes create the opportunity for comparing a series of complexes containing metal cations in the formal IV+ oxidation state by structural, spectroscopic, and theoretical analysis that also incorporate the previously reported Ce(IV) and Pu(IV) analogues. X-ray crystallographic analysis reveals that all complexes are isomorphous and feature a co-facial ligand geometry. TD-DFT and other quantum mechanical methods were used to explore bonding differences across between the complexes, and resulting calculated absorbance spectra for ML₂ are in good agreement with the experimental data. The computational results also suggest that U(IV) and Pu(IV) analogs have more covalent character in their bonding than found with the other metal cations reported here.