Issue 19, 2022

Generation of a transient base-stabilised arylalumylene for the facile deconstruction of aromatic molecules

Abstract

While a stable base-free arylalumylene bearing a sterically encumbered terphenyl substituent has been reported previously, we herein report that our attempts to form a base-stabilised arylalumylene bearing a relatively small terphenyl substituent and an N-heterocyclic carbene base led instead to a “masked” dialumene (LRAl[double bond, length as m-dash]AlRL), self-stabilised by one peripheral aromatic group. Intriguingly, examining the behavior of this species or its transient dialumene formed from reducing the diiodoarylalane in aromatic solvents under different conditions reveals that they both decouple into the desired base-stabilised arylalumylene. This transient acyclic, dicoordinate alumylene is highly reactive, deconstructing benzene and toluene to furnish dialuminium derivatives of pentalene, providing the first example of a neutral AlI compound able to deconstruct these less reactive arenes. Computational insights were also gained on the dialumene dissociation and on the mechanism of arene deconstruction by alumylene.

Graphical abstract: Generation of a transient base-stabilised arylalumylene for the facile deconstruction of aromatic molecules

Supplementary files

Article information

Article type
Edge Article
Submitted
11 Marts 2022
Accepted
25 Apr. 2022
First published
02 Maijs 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 5631-5638

Generation of a transient base-stabilised arylalumylene for the facile deconstruction of aromatic molecules

D. Dhara, A. Jayaraman, M. Härterich, R. D. Dewhurst and H. Braunschweig, Chem. Sci., 2022, 13, 5631 DOI: 10.1039/D2SC01436J

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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