Formation of fluorinated platinum-stilbazole complexes : Aryl-halide oxidative addition vs η2-coordination of a carbon-carbon double bond

Reaction of a zerovalent platinum complex with a partially fluorinated stilbazole ligand results in direct Arf−Br oxidation addition. The exclusive formation of the Arf−PtII−Br complex does not proceed via η2-CC coordination on the reaction coordinate or as a side-equilibrium prior to the observed C−Br bond activation. Arf−Br activation by Pt0 is the kinetically and most probably also the thermodynamically favorable process independent of the reaction temperature and solvent polarity. This is in stark contrast with the reactivity of isostructural nonfluorinated stilbazole systems, where there is a lower barrier for η2-CC coordination than for Ar−Br oxidative addition with Pt0.