The reactivity of palladium(0) complexes, [Pd-2(0),(dba-n,n'-Z)(3)] (n,n'-Z=4,4'-F; 4,4'-CF3; 4,4'-H; 4,4'-MeO) and [Pd-0(dba-n,n'-Z)(2)] (n,n'-Z=4,4'-CF3; 4,4'-H; 3,3',5,5'-OMe), used as precursor catalysts with suitable donor ligands (e.g. phosphines, N-heterocyclic carbenes), has been correlated in several palladium (0)-mediated cross-coupling processes. Increasing the electron density on the aryl moiety of the dban,n'-Z ligand increases the overall catalytic activity in the majority of these processes. This effect primarily derives from destabilization of the LnPd0-eta(2)dba interaction (in d pi-pi* synergic bonding, n=1 or 2), which ultimately increases the global concentration of catalytically active L,,Pd' available for reaction with aryl halide in the first committed step in the general catalytic cycle(s) (oxidative addition). Decreasing electron density on the aryl moiety of the dba-n,n'-Z ligand stabilizes the Pd-0-eta(2)-dba interaction, reducing catalytic activity. The specific type of dban,n'-Z ligand appears to also play a stabilizing role in the catalytic cycle, preventing I'd agglomeration, and increasing catalyst longevity. A subtle balance therefore exists between the LnPd0 concentration (and the associated catalytic activity) and catalyst longevity. Changing the type of dba-n,n'-Z ligand controls the concentration of LnPd0 and the rate of the oxidative addition step, and not other intimate steps within the catalytic cycle(s), for example, transmetallation (or carbopalladation) and reductive elimination. The role of dban,n'-Z ligands in Heck arylation is more convoluted and dependant on the alkene substrate employed, although trends have emerged. Changes in the structure of dba-n,n'-Z had a minimal affect on Buchwald-Hartwig aryl amination processes. A secondary Michael reaction of dba-n,n'-Z with amine and/ or base effectively lessens its interference in the catalytic cycle.