Issue 40, 2023

On the σ-complex character of bis(gallyl)/digallane transition metal species

Abstract

σ-complexes of homoatomic E–E bonds are key intermediates in catalytically relevant oxidative addition reactions, but are as yet unknown for the group 13 elements. Here, stable species best described as σ-complexes of a 1,2-dichlorodigallane derivative with Ni and Pd are reported. They are readily accessed through the combination of a 1,2-dichlorodigallane derivative, which features chelating phosphine functionalities, with Ni0 and Pd0 synthons. In-depth computational analyses of these complexes importantly reveal considerable Ga–Ga bonding interactions in both Ni and Pd complexes, despite the expected elongation of the Ga–Ga bond upon complexation, suggestive of σ-complex character as opposed to more commonly described bis(gallyl) character. Finally, the well-defined disproportion of the Ni complex is described, leading to a unique GaI–nickel complex, with concomitant expulsion of uncomplexed GaIII species.

Graphical abstract: On the σ-complex character of bis(gallyl)/digallane transition metal species

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Article information

Article type
Edge Article
Submitted
21 Jul 2023
Accepted
21 Sep 2023
First published
22 Sep 2023
This article is Open Access

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

Chem. Sci., 2023,14, 11088-11095

On the σ-complex character of bis(gallyl)/digallane transition metal species

T. L. Kalkuhl, L. Qin, L. Zhao, G. Frenking and T. J. Hadlington, Chem. Sci., 2023, 14, 11088 DOI: 10.1039/D3SC03772J

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