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

Abstract

The [3+1] fragmentation reaction of rare-earth metallacyclopentadienes 1 a-c with 0.5 equivalents of P affords a series of rare-earth metal cyclo-P complexes 2 a-c and a phospholyl anion 3. 2 a-c demonstrate an unusual η coordination mode with one P-P bond featuring partial π-bonding character. 2 a-c are the first cyclo-P complexes 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 Diels-Alder reaction. Compounds 2 a-c can coordinate to one or two [W(CO) ] units, yielding 4 a-c or 5 c, respectively. Furthermore, oxidation of 2 a with p-benzoquinone produces its corresponding phospholyllithium and regenerated P .

Black Phosphorus: An Effective Feedstock for the Synthesis of Phosphorus-Based Chemicals

“…5 Therefore, it is of both scientific and commercial interest to identify alternative synthetic techniques to directly convert low-toxic materials into valuable phosphoruscontaining compounds. Activation of P 4 by metal mediation [6][7][8][9][10] and direct conversion of phosphide anion 11 has recently been proposed to construct P-C bonds. Red phosphorus has also been used to synthesize some phosphorus-based chemicals.…”

Synthesis of a carborane-substituted bis(phosphanido) cobaltate(i), ligand substitution, and unusual P4fragmentation

“…Related transition-metal mediated [3+1] fragmentations of P4 have rarely been reported in the literature. 40,[44][45][46] To the best of our knowledge, our system is the first which incorporates both the resulting P3 and P1 fragment in the same product.…”

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

“…Solid-state structure of 2a. [22] Ellipsoids are set at 30 % probability;hydrogen atoms are omitted for clarity.S elected bond lengths []: C1-C2 1.500 (11), C2-C3 1.403 (12), C3-C4, 1.469 (12)…”

“…Solid-state structure of 4a. [22] Ellipsoids are set at 30 % probability;hydrogen atoms, lithium, and coordinating THF are omitted for clarity.S elected bond lengths []: W1-P1 2.547(2), Lu1-P1 2.621(2), Lu1-P2 3.024 (2), Lu1-P3 3.019 (2), Lu1-C1 2.372(8), Lu1-C2 2.571(8), Lu1-C3 2.563(8), Lu1-C4 2.368 (7), P1-P2 2.236 (3), P1-P3 2.247 (3), P2-P3 2.177 (3), P2-C1 1.850 (9), P3-C4 1.836 (9).…”