Reduction of Na+ within a {Mg2Na2} Assembly

Michael Hill; Han-Ying Dennis Liu; Sam Neale; Claire McMullin; Mary Mahon; Emma Richards

doi:10.1002/anie.202213670

Reduction of Na+ within a {Mg2Na2} Assembly

Michael Hill, Han-Ying Dennis Liu, Sam Neale, Claire McMullin, Mary Mahon, Emma Richards

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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 {Mg2Na2} 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 {Mg2Na2} ensemble, which arise exclusively from the 3s valence atomic orbitals of the constituent sodium and magnesium atoms.

Original language	English
Article number	e202213670
Number of pages	9
Journal	Angewandte Chemie International Edition
Volume	62
Issue number	3
Early online date	16 Nov 2022
DOIs	https://doi.org/10.1002/anie.202213670
Publication status	Published - 16 Jan 2023

Bibliographical note

We thank the EPSRC (EP/R020752/1) for support of this research. This research made use of theAnatra High Performance Computing (HPC) Service at the University of Bath.

Keywords

Density Functional Theory
Magnesium
Main Group Chemistry
Redox Chemistry
Sodium

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.202213670Licence: CC BY

Cite this

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title = "Reduction of Na+ within a {Mg2Na2} Assembly",

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 {Mg2Na2} 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 {Mg2Na2} ensemble, which arise exclusively from the 3s valence atomic orbitals of the constituent sodium and magnesium atoms.",

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author = "Michael Hill and Liu, {Han-Ying Dennis} and Sam Neale and Claire McMullin and Mary Mahon and Emma Richards",

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AU - Hill, Michael

AU - Liu, Han-Ying Dennis

AU - Neale, Sam

AU - McMullin, Claire

AU - Mahon, Mary

AU - Richards, Emma

N1 - We thank the EPSRC (EP/R020752/1) for support of this research. This research made use of theAnatra High Performance Computing (HPC) Service at the University of Bath.

PY - 2023/1/16

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N2 - 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 {Mg2Na2} 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 {Mg2Na2} ensemble, which arise exclusively from the 3s valence atomic orbitals of the constituent sodium and magnesium atoms.

AB - 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 {Mg2Na2} 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 {Mg2Na2} ensemble, which arise exclusively from the 3s valence atomic orbitals of the constituent sodium and magnesium atoms.

KW - Density Functional Theory

KW - Magnesium

KW - Main Group Chemistry

KW - Redox Chemistry

KW - Sodium

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Reduction of Na+ within a {Mg2Na2} Assembly

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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Nucleophilic alkaline earth boryls: from conception and theory to application

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Reduction of Na+ within a {Mg2Na2} Assembly

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

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Nucleophilic alkaline earth boryls: from conception and theory to application

Cite this