Cyclometalated 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” have 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.