Carbene-supported triphosphorus anion.

Mei, Yanbo; He, Xue-Yi; Li, Jiancheng; Liu, Mo; Liang, Qiuming; Yang, Chengbo; Liu, Liu Leo · Nat Commun · 2025

basic_science · Level V

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Abstract

The stabilization of reactive anionic main group species utilizing carbenes constitutes a burgeoning and scarcely explored field. Herein, we report the synthesis of an anionic triphosphorus [P<sub>3</sub>]- unit, supported by two cyclic (alkyl)(amino)carbenes (CAACs) in the form of potassium salts. This anion features a planar W-shaped conjugated C-P-P-P-C framework, characterized by 5-center-6-electron π delocalization and an additional σ lone pair located on each of the three phosphorus atoms. Remarkably, this anion is not only strongly basic and nucleophilic but also reductive, positioning versatile functionalization of the [P<sub>3</sub>] unit. This approach has advanced the isolation of unique carbene-supported cores, including [HP<sub>3</sub>], [P<sub>3</sub>N<sub>3</sub>R]<sup>-</sup>, [P<sub>3</sub>O]<sup>-</sup> and [P<sub>6</sub>], thus expanding the frontiers of phosphorus chemistry. Moreover, the addition of the two phosphorus fragments upon P-P bond cleavage of the [P<sub>3</sub>] unit to the triple bond of diphenylacetylene for the synthesis of an extended conjugated system was described.