The quantitative derails of three migratory insertion processes relevant to the copolymerization of ethylene and CO by the highly active (dppp)Pd(II)-based catalyst have been examined. Cationic Pd(II) intermediates generated at low temperatures and characterized by H-1, C-13 and P-31 NMR spectroscopy include (dppp)Pd(C2W4)(R)(+) (R = -CH3, -CH2CH3), 6 and 7; (dppp)Pd(CO)(R)(+) (R = -CH3, -CH2CH3), 8 and 11; acid (dppp)Pd(C2H4)(COCH3)(+), 13. Kinetic studies of the migratory insertion reactions of these species established the following activation parameters: 6(Delta G(double dagger) = 16.6(1) kcal/mol(-45.6 degrees C), Delta H-double dagger = 15.2(7) kcal/mol, Delta S-double dagger = -6.2(2.9) eu), 7(Delta G(double dagger) = 16.3(1) kcal/mol(-33.7 degrees C), Delta H-double dagger = 15.9(8) kcal/mol, Delta S-double dagger = -1.6(3.7) eu), 8(Delta G(double dagger) = 14.8(1) kcal/mol (-81.7 degrees C), Delta H-double dagger = 14.8(7) kcal/mol, Delta S-double dagger = 0.1(3.0) eu), 11(Delta G(double dagger) = 13.3(1) kcal/mol (-94.2 degrees C)), 13(Delta G(double dagger) = 12.3(1) kcal/mol (-103.1 degrees C)). On the basis of the relative binding affinities of CO and C2H4 to the Pd(II) center and the relative rates of alkyl to CO and alkyl to ethylene migratory insertion reactions, it can be estimated that sequential ethylene insertions occur only once in similar to 10(5) turnovers, thus corroborating the exceptionally high fidelity of the alternating copolymerization.