Issue 16, 2022

Unraveling differences in aluminyl and carbene coordination chemistry: bonding in gold complexes and reactivity with carbon dioxide

Abstract

The electronic properties of aluminyl anions have been reported to be strictly related to those of carbenes, which are well-known to be easily tunable via selected structural modifications imposed on their backbone. Since peculiar reactivity of gold-aluminyl complexes towards carbon dioxide has been reported, leading to insertion of CO2 into the Au–Al bond, in this work the electronic structure and reactivity of Au–Al complexes with different aluminyl scaffolds have been systematically studied and compared to carbene analogues. The analyses reveal that, instead, aluminyls and carbenes display a very different behavior when bound to gold, with the aluminyls forming an electron-sharing and weakly polarized Au–Al bond, which turns out to be poorly modulated by structural modifications of the ligand. The reactivity of gold–aluminyl complexes towards CO2 shows, both qualitatively and quantitatively, similar reaction mechanisms, reflecting the scarce tunability of their electronic structure and bond nature. This work provides further insights and perspectives on the properties of the aluminyl anions and their behavior as coordination ligands.

Graphical abstract: Unraveling differences in aluminyl and carbene coordination chemistry: bonding in gold complexes and reactivity with carbon dioxide

Supplementary files

Article information

Article type
Edge Article
Submitted
01 Feb 2022
Accepted
31 Mar 2022
First published
31 Mar 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, 4623-4634

Unraveling differences in aluminyl and carbene coordination chemistry: bonding in gold complexes and reactivity with carbon dioxide

D. Sorbelli, L. Belpassi and P. Belanzoni, Chem. Sci., 2022, 13, 4623 DOI: 10.1039/D2SC00630H

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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