Structure, Covalency, and Paramagnetism of Homoleptic Actinide and Lanthanide Amidinate Complexes

Isostructural trivalent lanthanide and actinide amidinates bearing the <i>N,N'</i>-bis(isopropyl)benzamidinate (<i>i</i>Pr₂BA) ligand [Ln^III/An^III(<i>i</i>Pr₂BA)₃] (Ln = La, Nd, Sm, Eu, Yb, Lu; An = U, Np) have been synthesized and characterized in both solid and solution states. All compounds were examined in the solid state utilizing single crystal X-ray diffraction (SC-XRD), revealing a notable deviation in the actinide series with shortened bond lengths compared to the trend in the lanthanide series, suggesting a nonionic contribution to the actinide-ligand bonding. Quantum-chemical bonding analysis further elucidated the nature of these interactions, highlighting increased covalency within the actinide series, as evidenced by higher delocalization indices and greater 5<i>f</i> orbital occupation, except for Th(III) and Pa(III), which demonstrated substantial 6<i>d</i> orbital occupancies. An in-depth paramagnetic NMR study in solution also sheds light on the covalent character of actinide-ligand bonding, with the separation of pseudocontact (PCS) and contact shift (FCS) contributions employing the Bleaney and Reilley method. This analysis unveiled significant contact contributions in the actinide complexes, indicating enhanced covalency in actinide-ligand bonding. To corroborate these observations, an accurate PCS calculation method based on the Kuprov equation, incorporating both the distribution of electronic spin density and magnetic susceptibility obtained from CASSCF calculations, was applied and compared with experimental values.