Researchers at Rice University have demonstrated a novel approach to lanthanide chemistry that could expand the toolkit available to synthetic chemists. The work focuses on achieving oxygen bonding with f-block metals, which occupy the bottom section of the periodic table and include lanthanides and actinides.
Assistant Professor Raúl Hernández Sánchez led the investigation into whether lanthanides could form highly reactive oxo compounds similar to those created with iron. Iron oxos are important in biological systems, including liver enzymes responsible for drug metabolism and hemoglobin’s oxygen-carrying function. The challenge facing researchers was that f-block metals, particularly lanthanides, were not thought to interact with small molecules like oxygen through pi interactions—bonding mechanisms crucial to many biological materials.
To overcome this limitation, the team employed a specially designed ligand structure described as a molecular basket capable of holding a single f-block metal atom. By positioning two baskets opposite each other with six connecting atoms and a dioxygen molecule between them, the researchers created an octacoordinate ligand environment that allowed precise positioning of the metal atoms. This configuration enabled neodymium, a lanthanide metal, to form pi interactions with dioxygen under specific conditions, producing the first observed lanthanide oxo compound through this mechanism.
The findings, reported in the Journal of the American Chemical Society, suggest that lanthanide oxos could serve as synthetic alternatives to iron oxos in chemical reactions and potentially offer unique capabilities unavailable through iron-based compounds. The research team expects the same ligand platform could facilitate similar reactions with most other lanthanides and likely actinides as well.
The study was funded through startup support from Rice University and grants from the Robert A. Welch Foundation, which aims to advance fundamental chemical research in Texas.
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