Electronic structure and bonding studies involving lanthanide (Ln) and actinide (Ac) complexes have been of significant interest to the chemistry community for decades. Electron paramagnetic resonance (EPR) can be significant asset in trying to understand the electronic structure of various Ln and Ac complexes. Ligands containing EPR active nuclei, such as phosphorus (31P has I = 1/2), can be rationally designed, providing further electronic information regarding hyperfine coupling interactions with the metal center. Further, phosphorus-based ligand motifs can provide stabilization towards a series of Ln and Ac complexes, allowing for the synthesis of these f-block containing complexes with varying multiple oxidation states. Ln centers are typically limited to the Ln3+ oxidation, however, rare structures of Ce4+, Tb4+, and Pr4+ complexes have been synthesized in recent years. Having access to a series of Ln complexes across multiple oxidation states containing the same ligand motif is critical for the understanding of covalency and reactivity in Ln and Ac complexes. Phosphorus-containing ligands have been successful in aiding the synthesis of such a series, and have been characterized by EPR when appropriate.

Structure, reactivity, and electronic structure studies of f-block elements with phosphorus containing ligands

ACS Spring Meeting 2021

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