Dual Functionalization of White Phosphorus: Formation, Characterization, and Reactivity of Rare-Earth-Metal Cyclo-P-3 Complexes

摘要

The [3+1] fragmentation reaction of rare-earth metallacyclopentadienes 1a-c with 0.5equivalents of P-4 affords a series of rare-earth metal cyclo-P-3 complexes 2a-c and a phospholyl anion 3. 2a-c demonstrate an unusual (3) coordination mode with one P-P bond featuring partial -bonding character. 2a-c are the first cyclo-P-3 complexes of rare-earth metals, and also the first organo-substituted polyphosphides in the category of Group3 and f-block elements. Rare-earth metallacyclopentadienes play a dual role in the combination of aromatization and Diels-Alder reaction. Compounds 2a-c can coordinate to one or two [W(CO)(5)] units, yielding 4a-c or 5c, respectively. Furthermore, oxidation of 2a with p-benzoquinone produces its corresponding phospholyllithium and regenerated P-4.