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

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Abstract

The cationic magnesium moiety of magnesium organohaloaluminate 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.

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Brouillet, E. V., Kennedy, A. R., Koszinowski, K., McLellan, R., Mulvey, R. E., & Robertson, S. D. (2016). Exposing elusive cationic magnesium-chloro aggregates in aluminate complexes through donor control. Dalton Transactions, 45(13), 5590–5597. https://doi.org/10.1039/c6dt00531d

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