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Exploring Equilibria between Aluminium(I) and Aluminium(III): The Formation of Dihydroalanes, Masked Dialumenes and Aluminium(I) Species

Bakewell, Clare; Hobson, Katie; Carmalt, Claire J; (2022) Exploring Equilibria between Aluminium(I) and Aluminium(III): The Formation of Dihydroalanes, Masked Dialumenes and Aluminium(I) Species. Angewandte Chemie International Edition , Article e202205901. 10.1002/anie.202205901. (In press). Green open access

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Abstract

The design of new reductive routes to low oxidation state aluminium (Al) compounds offers the opportunity to better understand redox processes at the metal centre and develop reactivity accordingly. Here, a monomeric AlI compound acts as a stoichiometric reducing agent towards a series of AlIII dihydrides, leading to the formation of new low oxidation state species including symmetric and asymmetric dihydrodialanes, and a masked dialumene. These compounds are formed by a series of equilibrium processes involving AlI, AlII and AlIII species and product formation can be manipulated by fine-tuning the reaction conditions. The transient formation of monomeric AlI compounds is proposed: this is shown to be energetically viable by computational (DFT) investigations and reactivity studies show support for the formation of AlI species. Importantly, despite the potential for the equilibrium mixtures to lead to ill-defined reactivity, controlled reactivity of these low oxidation state species is observed.

Type: Article
Title: Exploring Equilibria between Aluminium(I) and Aluminium(III): The Formation of Dihydroalanes, Masked Dialumenes and Aluminium(I) Species
Location: Germany
Open access status: An open access version is available from UCL Discovery
DOI: 10.1002/anie.202205901
Publisher version: https://doi.org/10.1002/anie.202205901
Language: English
Additional information: © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/).
Keywords: Aluminium, Low Oxidation State, Masked Dialumene, Redox, Reversible
UCL classification: UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL
URI: https://discovery.ucl.ac.uk/id/eprint/10149859
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