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Herein, we disclose the facile reduction of pyridine (and its derivatives) by linear 3d‐metal(I) silylamides (M=Cr–Co). This reaction resulted in intermolecular C−C coupling to give dinuclear metal(II) complexes bearing a bridging 4,4′‐dihydrobipyridyl ligand. For iron, we demonstrated that the C−C coupling is reversible in solution, either directly or by reaction with substrates, via a presumed monomeric metal(II) complex bearing a pyridyl radical anion. In the course of this investigation, we also observed that the dinuclear metal(II) complex incorporating iron facilitated the isomerisation of 1,4‐cyclohexadiene to 1,3‐cyclohexadiene as well as equimolar amounts of benzene and cyclohexene. Furthermore, we synthesised and structurally characterised a non‐3d‐metal‐bound pyridyl radical anion. The reactions of the silylamides with perfluoropyridine led to C−F bond cleavage with the formation of metal(II) fluoride complexes of manganese, iron and cobalt along with the homocoupling or reductive degradation of the substrate. In the case of cobalt, the use of lesser fluorinated pyridines led to C−F bond cleavage but no homocoupling. Overall, in this paper we provide insights into the multifaceted behaviour of simple (fluoro)pyridines in the presence of moderately to highly reducing metal complexes.

chemistry – a european journal

Reductive Coupling of (Fluoro)pyridines by Linear 3d‐Metal(I) Silylamides of Cr–Co: A Tale of C−C Bond Formation, C−F Bond Cleavage and a Pyridyl Radical Anion