What question did this study set out to answer?

The aim is to explore synthetic routes for developing novel phosphorus-containing anions from white phosphorus.

April 5, 2026Open Access

Synthetic Pathways Towards 1,3,4‐Tri‐ and Tetraphospholide Anions from White Phosphorus and Polyphosphides

MEMoritz ErnstFreie Universität Berlin APAndrey PetrovLeibniz Institute for Catalysis MWManuela WeberFreie Universität Berlin

Key Points

The aim is to explore synthetic routes for developing novel phosphorus-containing anions from white phosphorus.
Generated sodium polyphosphides from white phosphorus and sodium.
Reacted polyphosphides with phosphaalkynes to form triphosphacyclopentadienides and tetraphosphacyclopentadienides.
Conducted one-pot reactions with carboxylic acids to obtain bis(acyl)phosphides and tetraphosphacyclopentadienides.
Successfully synthesized sodium 1,3,4-triphosphacyclopentadienide and tetraphosphacyclopentadienide.
The reactions yielded mixtures that could be separated, demonstrating versatility in product formation.
Generated potential precursors for tetraphosphaferrocenes with Fe II.

Abstract

Sodium polyphosphides Na x P n (Na cyclo ‐P 5 and Na 3 P 7 ), generated from white phosphorus and elemental sodium, react with phosphaalkynes R–C≡P (R = SiMe 3 , t Bu, Ad, Mes) to give the respective sodium 2,5‐R‐1,3,4‐triphosphacyclopentadienide Na1,3,4‐( cyclo ‐(CR) 2 P 3 either solely, or as a mixture with the corresponding 1,2,3,4‐tetraphosphacyclopentadienide Na( cyclo ‐(CR)P 4 . The one‐pot reaction between Na, P 4 , and carboxylic acid derivatives (acyl chlorides or esters) leads to a mixture that mainly consists of sodium bis(acyl)phosphides Na(C(O)R) 2 P and 1,2,3,4‐tetraphosphacyclopentadienides Na( cyclo ‐(CR)P 4 (R = Ar, Alk, ), which can be separated. ( cyclo ‐(CR)P 4 – anions represent a class of scarcely investigated aromatic phosphorus‐heterocycles that are of considerable interest in coordination chemistry. Further studies show the possibilities to generate tetraphosphaferrocenes when treated with Fe II precursors.

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