Linear Open-Shell 3d-Metal Silylamides – A Versatile Tool in Coordination Chemistry

Abstract

Linear 3d-metal complexes with open-shell metal ions have fascinated coordination chemists for decades. Originally the focus lied on metal(II) species, yet the synthetic possibilities to acquire their reduced analogues, together with the introduction of NHC’s as stabilizing co-ligands, has expanded the structural knowledge and feasible oxidation states to +I and even 0. Despite a certain wealth of structural data, the knowledge about the reactivity or even catalytic applications of such compounds remained comparably thin for a long time given the intrinsic lability of these coordinatively and electronically unsaturated compounds. In this feature article we review the emerging chemistry and reactivity of silylamide based complexes, as mostly for these a comprehensive, broader picture of their reactivity patterns has been developed in recent years. Together with related, selected reactivity examples of other linear metal complexes, the review shall serve as an entry point for interested molecular organic/inorganic chemists to join the scientific endeavour within this field.