Room Temperature Rapid Functionalization of E–H Bonds (E = O, N, S) via the Metal–Ligand Cooperation Mechanism

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.