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

Till L. Kalkuhl, Lei Qin, Lili Zhao, Gernot Frenking, Terrance J. Hadlington

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1 引用 (Scopus)

摘要

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.

源语言英语
页(从-至)11088-11095
页数8
期刊Chemical Science
14
40
DOI
出版状态已出版 - 22 9月 2023

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