An arylpalladium PNF-type pincer complex reacts with water and anilines under very mild conditions, providing access to new PNO- and PNN-pincer complexes with concomitant hydrogen transfer to the ligand core. Such a metal-ligand cooperation mode allows for the irreversible double activation of even highly sterically hindered aniline molecules. With thiols, the activation mode depends on the nature of the substituent at the sulfur atom, with thiophenols giving products of C-S elimination.