A series of monomeric palladium amido complexes of the form trans-(PPh3)(2)Pd(Ar)(NAr'(2)) and (DPPF)-Pd(Ar)(NAr'(2)) (DPPF = 1,1'-bis(diphenylphosphino)ferrocene) and dimeric palladium amido complexes of the form {(PPh3)Pd(Ar)(mu-NHR)}(2) (R = Ph, t-Bu) have been prepared by the reaction of lithium and potassium amides with palladium aryl halide complexes, An X-ray crystal structure of (DPPF)Pd(p-NMe2C6H4)[N(p-CH3C6H4)(2)] was obtained. Upon thermolysis in the presence of PPh3, serving as a trapping agent, both the monomeric and dimeric palladium amido complexes underwent C-N-bond-forming reductive elimination to form arylamines in high yields along with a Pd(0) species. Reductive elimination was also observed from azametallacycle (PPh3)Pd(eta(2)-C6H4C6H4- NH), to form carbazole and Pd(PPh3)(4) at room temperature. Mechanistic studies on the reductive elimination reactions of the monomeric PPh3-ligated amido complexes indicated the presence of two competing pathways for the formation of amine. At low [PPh3], reductive elimination occurs via phosphine dissociation to form a three-coordinate intermediate; however, as [PPh3] is increased, a pathway of reductive elimination from a four-coordinate complex becomes dominant. The DPPF-ligated palladium amido complexes directly eliminated amine from the four-coordinate complex. The mechanism of the reductive elimination from dimeric palladium amido complexes was also studied. These complexes undergo reductive elimination of amine via dimer dissociation to generate a three-coordinate intermediate analogous to those formed by the PPh3-ligated monomeric amido complexes. The C-N-bond forming reductive elimination reactions were accelerated by electron-withdrawing groups on the Pd bound aryl group and by electron-donating groups on the amido ligand, suggesting that the aryl group acts as an electrophile and the amido ligand acts as a nucleophile.