Carbon‐Phosphorus Cross‐Anion Coupling on Rare‐Earth Center

ABSTRACT Carbon‐phosphorus cross‐anion coupling reaction on rare‐earth center is implemented through formal reductive elimination process. Phosphine oxides with different substituents are treated to prove the universality of this method. Computational approaches are applied to confirm that the reaction generated a C═P double bond during the process, and the two‐electron reductive elimination process occurs with the assistance of the butadienyl backbone. The orbital interactions of the key transition states are clarified by principal interacting orbital (PIO) analysis. This work significantly expands the applicability of rare‐earth metallacycles and further reveals their unique reactivity, providing a C─P coupling, azametallacycle, metallacycle, rare‐earth metal novel strategy for constructing phosphorus‐containing compounds.