Exposing elusive cationic magnesium-chloro aggregates in aluminate complexes through donor control

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Brouillet, Etienne V. and Kennedy, Alan R. and Koszinowski, Konrad and McLellan, Ross and Mulvey, Robert E. and Robertson, Stuart D. (2016) Exposing elusive cationic magnesium-chloro aggregates in aluminate complexes through donor control. Dalton Transactions, 45 (13). pp. 5590-5597. ISSN 1477-9226 (https://doi.org/10.1039/c6dt00531d)

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Abstract

The cationic magnesium moiety of magnesium organohalo aluminate complexes, relevant to rechargeable Mg battery electrolytes, typically takes the thermodynamically favourable dinuclear [Mg2Cl3]+ form in the solid-state. We now report that judicious choice of Lewis donor allows the deliberate synthesis and isolation of the hitherto only postulated mononuclear [MgCl]+ and trinuclear [Mg3Cl5]+ modifications, forming a comparable series with a common aluminate anion [(Dipp)(Me3Si)NAlCl3]. By pre-forming the Al-N bond prior to introduction of the Mg source, a consistently reproducible protocol is reported. Usage of the green solvent 2-methyltetrahydrofuran in place of THF in the context of Mg/Al battery electrolyte type complexes is also promoted.

ORCID iDs

Brouillet, Etienne V. ORCID logoORCID: https://orcid.org/0000-0001-5854-1983, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Koszinowski, Konrad, McLellan, Ross ORCID logoORCID: https://orcid.org/0000-0001-9700-0258, Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564 and Robertson, Stuart D. ORCID logoORCID: https://orcid.org/0000-0002-9330-8770;
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