text: Most asymmetric Heck reactions employing chiral phosphines proceed by the cationic pathway, which does not require the dissociation of a phosphine ligand. Oxidative addition of an aryl perfluorosulfonate generates a cationic palladium aryl complex V. The mechanism then proceeds as in the neutral case, with the difference that an extra site of coordinative unsaturation exists on palladium throughout the process. 
  Thus, coordination of the alkene does not require ligand dissociation. Stoichiometric amounts of base are still required to reduce the palladium(II)-hydrido complex VIII back to palladium(0). Silver salts may be used to initiate the cationic pathway in reactions of aryl halides.