Electronic structure studies reveal 4f/5d mixing and its effect on bonding characteristics in Ce-imido and -oxo complexes

This study presents the role of 5d orbitals in the bonding, and electronic and magnetic structure of Ce imido and oxo complexes synthesized with a tris(hydroxylaminato) [((2-(BuNO)-Bu-t)C6H4CH2)(3)N](3-) (TriNO(x)(3-)) ligand framework, including the reported synthesis and characterization of two new alkali metal-capped Ce oxo species. X-ray spectroscopy measurements reveal that the imido and oxo materials exhibit an intermediate valent ground state of the Ce, displaying hallmark features in the Ce L-III absorption of partial f-orbital occupancy that are relatively constant for all measured compounds. These spectra feature a double peak consistent with other formal Ce(iv) compounds. Magnetic susceptibility measurements reveal enhanced levels of temperature-independent paramagnetism (TIP). In contrast to systems with direct bonding to an aromatic ligand, no clear correlation between the level of TIP and f-orbital occupancy is observed. CASSCF calculations defy a conventional van Vleck explanation of the TIP, indicating a single-reference ground state with no low-lying triplet excited state, despite accurately predicting the measured values of f-orbital occupancy. The calculations do, however, predict strong 4f/5d hybridization. In fact, within these complexes, despite having similar f-orbital occupancies and therefore levels of 4f/5d hybridization, the d-state distributions vary depending on the bonding motif (Ce=O vs. Ce=N) of the complex, and can also be fine-tuned based on varying alkali metal cation capping species. This system therefore provides a platform for understanding the characteristic nature of Ce multiple bonds and potential impact that the associated d-state distribution may have on resulting reactivity.

Automated summary

This study examines the role of 5d orbitals in Ce imido and oxo complexes and their impact on bonding, electronic, and magnetic structure. The results show that the distribution of d states varies depending on the bonding motif and capping species, despite similar occupancy levels of f orbitals.