In the Heck reaction between aryl halides and n-butyl acrylate, the palladacycle {Pd[kappa(1)-C, kappa(1)-N-C=(C6H5)C(CI)CH2NMe2](mu-Cl)}(2), 1, is merely a reservoir of the catalytically active Pd(0) species [1] (Pd colloids or highly active forms of low ligated Pd(0) species) that undergoes oxidative addition of the aryl halide on the surface with subsequent detachment, generating homogeneous Pd(II) species. The main catalytic cycle is initiated by oxidative addition of iodobenzene to [1], followed by the reversible coordination of the olefin to the oxidative addition product. All the unimolecular subsequent steps are indistinguishable kinetically and can be combined in a single step. This kinetic model predicts that a slight excess of alkene relative to iodobenzene leads to a rapid rise in the Pd(0) concentration while when using a slight excess of iodobenzene, relative to alkene, the oxidative addition product is the resting state of the catalytic cycle. Competitive experiments of various bromoarenes and iodoarenes with n-butyl acrylate catalyzed by 1 and CS, CP, and NCN palladacycles gave the same rho value (2.4-2.5 for Ar-Br and 1.7-1.8 for Ar-I) for all palladacycles employed, indicating that they generate the same species in the oxidative addition step. The excellent fit of the slope with the sigma(0) Hammett parameter and the entropy of activation of -43 +/- 8 J mol(-1) K-1 are consistent with an associative process involving the development of only a partial charge in the transition state for the oxidative step of iodobenzene.