Generation of a π-Bonded Isomer of [P4 ]4- by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3.
Angew Chem Int Ed Engl
; 60(51): 26550-26554, 2021 Dec 13.
Article
in En
| MEDLINE
| ID: mdl-34677901
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 P4 2- and P4 4- 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 P4 4- 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).
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Angew Chem Int Ed Engl
Year:
2021
Document type:
Article
Affiliation country:
United kingdom