Issue 28, 2022

The crucial and multifaceted roles of main-group cations and their salts in iron-mediated cross-couplings

Abstract

While a broad variety of iron-catalyzed cross-couplings involve the use of main-group organometallics R–[M] as nucleophiles, the role of the [M]n+ cation in the coupling process is generally disregarded. However, several beneficial effects of [M]n+ cations by themselves or involved in ionic salts used as additives have been observed in such procedures. At the molecular level, interaction of those [M]n+ cations with on-cycle organoiron intermediates can proceed in several ways. Intermolecular interactions can be observed, and also the implication of [M]n+ in the iron's first or second coordination sphere, e.g. by ambiphilic coordination of a [M]–X salt to an R–[Fe] bond. The use of [M]n+ cations in the reaction medium is also a powerful strategy enabling control of the distribution of iron oxidation states within the coupling process.

Graphical abstract: The crucial and multifaceted roles of main-group cations and their salts in iron-mediated cross-couplings

Article information

Article type
Frontier
Submitted
21 3 2022
Accepted
28 4 2022
First published
04 5 2022

Dalton Trans., 2022,51, 10674-10680

The crucial and multifaceted roles of main-group cations and their salts in iron-mediated cross-couplings

V. Wowk and G. Lefèvre, Dalton Trans., 2022, 51, 10674 DOI: 10.1039/D2DT00871H

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