Cyclometallated complexes of transition metals have received considerable attention since 1960s, in particular as the reactive intermediates of catalytic C-H functionalizations. However, only recently the unique catalytic properties of few bench stable complexes bearing anionic “carboligands” has been discovered. This presentation will discuss the rational design of anionic C,N-ligands allowing for novel catalytic transformations. Our recent applications of iridium – ketimine catalysts towards acid-assisted ionic hydrogenation of oximes to hydroxylamines, anhydride-assisted amide hydrogenation and regioselective C-H-borylation will be highlighted.

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