Generation of a π‐Bonded Isomer of [P4]4− by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3
By employing the highly reducing aluminyl complex [K{(NON)Al}]2 (NON=4,5‐bis(2,6‐diisopropylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene), we demonstrate the controlled formation of P42− and P44− complexes from white phosphorus, and chemically reversible inter‐conversion between them. The tetra‐a...
Gespeichert in:
Veröffentlicht in: | Angewandte Chemie International Edition 2021-12, Vol.60 (51), p.26550-26554 |
---|---|
Hauptverfasser: | , , , |
Format: | Artikel |
Sprache: | eng |
Schlagworte: | |
Online-Zugang: | Volltext |
Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
Zusammenfassung: | By employing the highly reducing aluminyl complex [K{(NON)Al}]2 (NON=4,5‐bis(2,6‐diisopropylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene), we demonstrate the controlled formation of P42− and P44− complexes from white phosphorus, and chemically reversible inter‐conversion between them. The tetra‐anion features a unique planar π‐bonded structure, with the incorporation of the K+ cations implicit in the use of the anionic nucleophile offering additional stabilization of the unsaturated isomer of the P44−fragment. This complex is extremely reactive, acting as a source of P3−: exposure to ammonia leads to the release of phosphine (PH3) under mild conditions (room temperature and pressure), which contrast with those necessitated for the direct combination of P4 and NH3 (>5 kbar and >250 °C).
The reduction of white phosphorus by an aluminum(I) anion is explored. The four‐electron reduction product serves as a means of phosphine gas production on exposure to ammonia. |
---|---|
ISSN: | 1433-7851 1521-3773 |
DOI: | 10.1002/anie.202112515 |