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

Clare Bakewell*, Katie Hobson, Claire J. Carmalt

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

14 Citations (Scopus)

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.

Original languageEnglish
Article numbere202205901
JournalAngewandte Chemie - International Edition
Volume61
Issue number31
DOIs
Publication statusPublished - 1 Aug 2022

Keywords

  • Aluminium
  • Low Oxidation State
  • Masked Dialumene
  • Redox
  • Reversible

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