Research news, Dec. 9th, 2017

Dual Functionalization of White Phosphorus: Formation, Characterization, and Reactivity of Rare-Earth-Metal Cyclo-P3 Complexes

Shanshan Du, Jianhao Yin, Yue Chi, Ling Xu, and Wen-Xiong Zhang*

Angew. Chem. Int. Ed. 2017, 56, 15886–15890.

The direct functionalization of white phosphorus constructing value-added phosphorus-containing compounds is becoming a hot area. In this paper, we report the [3+1]-fragmentation reaction of rare-earth metallacyclopentadienes with 0.5 equivalents of P4 which affords a series of rare-earth metal cyclo-P3complexes and phospholyl anion. Rare-earth metal cyclo-P3 complexes demonstrate an unusual η3coordination mode with one P-P bond featuring partial π bonding character, which are the first cyclo-P3complexes of rare-earth metals, and also the first organo-substituted polyphosphides in the category of group 3 and f-block elements. Rare-earth metallacyclopentadienes play a dual role in the combination of aromatization and D-A reaction. Reaction chemistry studies reveal that compounds rare-earth metal cyclo-P3 complexes could coordinate to one or two [W(CO)5] units yielding the corresponding complexes, respectively. Furthermore, oxidation of rare-earth metal cyclo-P3 complex with p-benzoquinone produces its corresponding phospholyl lithium and regenerated P4.