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- Title
Generation of a π‐Bonded Isomer of [P<sub>4</sub>]<sup>4−</sup> by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH<sub>3</sub>.
- Authors
Roy, Matthew M. D.; Heilmann, Andreas; Ellwanger, Mathias A.; Aldridge, Simon
- Abstract
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).
- Subjects
AMMONOLYSIS; ISOMERS; PHOSPHORUS; PHOSPHINE; AMMONIA; ATMOSPHERIC ammonia
- Publication
Angewandte Chemie, 2021, Vol 133, Issue 51, p26754
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202112515