Synthesis and Reactivity of Rare-earth Metal Phosphaethynolates

Over the course of the last six years, research on the synthesis and reactivity of molecular metal phosphaketenes (M-PCO) has gained increasing attention. However, lanthanide complexes of the heavier group 15 cyanate analogue PCO have not been investigated so far. Herein we present exemplar studies on the nature and reactivity of rare-earth phosphaethynolato-complexes using three characteristic representatives of the rare-earth metals: Y, Nd and Sm. Our investigations comprise both +2 and +3 redox states, and one defined amidinate-based ligand set, as well as novel reaction pathways in the presence of the sequestering agents 18-crown-6 and 2,2,2-crypt.