In:
Angewandte Chemie, Wiley, Vol. 135, No. 3 ( 2023-01-16)
Abstract:
Ionic compounds containing sodium cations are notable for their stability and resistance to redox reactivity unless highly reducing electrical potentials are applied. Here we report that treatment of a low oxidation state {Mg 2 Na 2 } species with non‐reducible organic bases induces the spontaneous and completely selective extrusion of sodium metal and oxidation of the Mg I centers to the more conventional Mg II state. Although these processes are also characterized by a structural reorganisation of the initially chelated diamide spectator ligand, computational quantum chemical studies indicate that intramolecular electron transfer is abetted by the frontier molecular orbitals (HOMO/LUMO) of the {Mg 2 Na 2 } ensemble, which arise exclusively from the 3 s valence atomic orbitals of the constituent sodium and magnesium atoms.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.202213670
Language:
English
Publisher:
Wiley
Publication Date:
2023
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